TR2023006438T2 - DARK BLUE TO BLACK REACTIVE PAINT COMPOSITION AND ITS PAINT PRODUCT - Google Patents
DARK BLUE TO BLACK REACTIVE PAINT COMPOSITION AND ITS PAINT PRODUCTInfo
- Publication number
- TR2023006438T2 TR2023006438T2 TR2023/006438 TR2023006438T2 TR 2023006438 T2 TR2023006438 T2 TR 2023006438T2 TR 2023/006438 TR2023/006438 TR 2023/006438 TR 2023006438 T2 TR2023006438 T2 TR 2023006438T2
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- Prior art keywords
- formula
- component
- dark blue
- group
- independently
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Links
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 239000003973 paint Substances 0.000 title claims abstract description 12
- 239000000975 dye Substances 0.000 claims abstract description 119
- -1 alkali metal salts Chemical class 0.000 claims abstract description 96
- 150000001875 compounds Chemical class 0.000 claims abstract description 92
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 77
- 239000000985 reactive dye Substances 0.000 claims abstract description 66
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 70
- 229910006069 SO3H Inorganic materials 0.000 claims description 55
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 43
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 241000282887 Suidae Species 0.000 claims description 18
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 102220043690 rs1049562 Human genes 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- 125000004957 naphthylene group Chemical group 0.000 claims 2
- 101000938567 Homo sapiens Persulfide dioxygenase ETHE1, mitochondrial Proteins 0.000 claims 1
- 102100030940 Persulfide dioxygenase ETHE1, mitochondrial Human genes 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 39
- 239000004744 fabric Substances 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 8
- 239000002657 fibrous material Substances 0.000 abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 26
- 238000005859 coupling reaction Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 239000012954 diazonium Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 238000006193 diazotization reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 210000002268 wool Anatomy 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 239000000546 pharmaceutical excipient Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 3
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- FOINSAWEWXUXPQ-UHFFFAOYSA-N 4-acetamido-2-aminobenzenesulfonic acid Chemical compound CC(=O)NC1=CC=C(S(O)(=O)=O)C(N)=C1 FOINSAWEWXUXPQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WODGMMJHSAKKNF-UHFFFAOYSA-N 2-methylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WODGMMJHSAKKNF-UHFFFAOYSA-N 0.000 description 1
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- ZLBAMQINIRRJEN-UHFFFAOYSA-N benzyl naphthalene-1-sulfonate Chemical compound C=1C=CC2=CC=CC=C2C=1S(=O)(=O)OCC1=CC=CC=C1 ZLBAMQINIRRJEN-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004045 reactive dyeing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Abstract
LACİVERTTEN SİYAHA REAKTİF BOYA BİLEŞİMİ VE BUNUN BOYA ÜRÜNÜ. Mevcut buluşta, lacivertten siyaha reaktif bir boya bileşimi açıklanmaktadır. Lacivertten siyaha reaktif boya bileşimi A bileşenini ve B bileşenini içerir; burada A bileşeni formül (I) boya bileşikleri ve bunların alkali metal tuzlarından oluşan gruptan seçilen bir veya birkaçıdır ve B bileşeni formül (II) boya bileşikleri ve bunların alkali metal tuzlarından oluşan gruptan seçilen bir veya birkaçıdır; A ve B bileşenine göre, A bileşeninin kütle itibariyle oranı %5 ila %50`tir ve B bileşeninin kütle itibariyle oranı %50 ila %95?tir. Mevcut buluş aynı zamanda lacivertten siyaha reaktif boya bileşimini içeren lacivertten siyaha reaktif boya ürünü de sağlamaktadır. İyi yıkama haslığı, yüksek derecede fiksaj ve iyi birikme gibi niteliklere sahip olan lacivertten siyaha reaktif boya bileşimi ve boya ürünü, azot içeren ve/veya hidroksil içeren elyaf malzemelerin ve bunların karışımlı kumaşlarının basılması ve boyanması için uygundur.DARK BLUE TO BLACK REACTIVE PAINT COMPOSITION AND ITS PAINT PRODUCT. The present invention discloses a dark blue to black reactive dye composition. The dark blue to black reactive dye composition includes component A and component B; wherein component A is one or more selected from the group consisting of dye compounds of formula (I) and alkali metal salts thereof, and component B is one or more selected from the group consisting of dye compounds of formula (II) and alkali metal salts thereof; According to components A and B, the mass fraction of component A is 5% to 50%, and the mass fraction of component B is 50% to 95%. The present invention also provides a dark blue to black reactive dye product comprising a dark blue to black reactive dye composition. The dark blue to black reactive dye composition and dye product, which has qualities such as good washing fastness, high degree of fixation and good deposition, is suitable for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials and their blended fabrics.
Description
TARIFNAME LACIVERTTEN SIYAHA REAKTIF BOYA BILESIMI VE BUNUN BOYA ÜRÜNÜ Teknik Alan Mevcut bulus, reaktif bir boya bilesimi ve bunun boya ürünü, bilhassa azot içeren ve/veya hidroksil içeren elyaf malzemelerin basilmasi ve boyanmasi için uygun reaktif bir lacivert- siyah boya bilesimi ve bunun boya ürünü ile ilgilidir. Arka Plan Teknigi Reaktif siyah boya KNB, düsük fiyati, iyi hasliklari ve kolay yikanmasi nedeniyle en yaygin kullanilan reaktif siyah boya haline gelmistir. Bununla birlikte, boyanin elyafa substantivitesi düsüktür ve boya emilimi ve fiksaj derecesi yüksek degildir. Reaktif siyah boya KNB'nin eksikliklerini hedefleyen boya arastirmacilari, son yillarda reaktif siyah boyalarin arastirilmasi ve gelistirilmesi konusunda birçok çalisma yapmistir. Gerçek uygulama sürecinde, CN reaktif siyah ürünler hala zayif birikme ve iyi olmayan yikama hasligi gibi sorunlara sahiptir. Bulusun Özeti Yukaridaki sorunlari çözmek için, mevcut bulusun hedefi, azot içeren ve/veya hidroksil içeren elyaf malzemelerin ve bunlarin karisimli kumaslarinin basilmasi ve boyanmasi için uygun olan, iyi yikama hasligi, yüksek derecede fiksaj ve iyi birikme gibi niteliklere sahip lacivertten siyaha reaktif boya bilesimi ve boya ürünü saglamaktir. Yukaridaki hedefe ulasmak için, mevcut bulus söyle bir teknik çözüm benimsemektedir: Mevcut bulus, Abileseni ve B bileseni içeren lacivertten siyaha reaktif bir boya bilesimi saglar; burada A bileseni, formül (I) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen biri veya birkaçidir ve B bileseni, formül (II) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen biri veya birkaçidir; A bileseni ve B bilesenine göre, A bileseninin kütle itibariyle orani %5 ila %50 arasindadir ve B bileseninin kütle itibariyle Formül (I)'de: D1 ve Dz'nin her biri bagimsiz olarak asagidaki formül (a) veya formül (b) ile temsil edilen bir R5 (a) X (b) Yukaridaki formül (I), formül (a) ve formül (b)'de: R1 ve Rz'nin her biri bagimsiz olarak hidrojen, oksijen, -COR7, C1 iIa C4 aIkiI veya hidroksil, sülfo veya karboksil iIe ikame edilmis C1 iIa C4 aIkiIdir, burada R7 C1 iIa C aIkiI, C2 iIa C4 aIkeniI veya -NH2'dir; R3 hidrojen, C1 iIa C4 aIkiI, C1 iIa C4 aIkoksi, karboksil veya sülfo'dur; R4 iIa Rö'nin her biri bagimsiz olarak hidrojen, C1 iIa C4 aIkiI, C1 iIa C4 aIkoksi veya sülfo'dur; X1 ve X2'nin her biri bagimsiz olarak -SOzY1 , -NHCO(CH2)p802Y2 veya - CONH(CH2)q802Y3'tür, burada Y1 iIa Y3'ün her biri bagimsiz olarak -CH=CH2` - formül (II)'de: R8 iIa R"'in her biri bagimsiz olarak hidrojen, C1 iIa C4 aIkiI, C1 iIa C4 aIkoksi veya sülfo'dur; Mevcut bulusta, C1 iIa C4 aIkiI metiI, etil, n-propil, izopropil, n-bütiI, izobütiI, tert-bütil, vb. olabilir; C1 ila C4 alkoksi metoksi, etoksi, n-propoksi, izopropoksi, n-bütoksi, izobütoksi, tert-bütoksi, vb. olabilir. Ayrica, hem D1 hem de D2 tercihen formül (a) veya formül (b) grubudur. Daha da ötesi, hem D1 hem de D2 tercihen formül (a) grubudur. Ayrica, R1 ve Rz'nin her biri bagimsiz olarak tercihen hidrojen veya -COR7'dir, burada R7 metil veya -NH2'dir. Ayrica, R3 tercihen hidrojen, metil, metoksi, karboksil veya sülfo'dur. Ayrica, R4 ila Rö'nin her biri bagimsiz olarak tercihen hidrojen, metil, metoksi veya sülfo'dur. Ayrica, X1 ve X2'nin her biri bagimsiz olarak tercihen -SOzY1 , -NHCOCH2CH2802Y2 veya - CONHCH2CH2802Y3'tür, burada Y1 ila Y3'ün her biri bagimsiz olarak -CH=CH2 veya - CH2CH20803H'dIr. Ayrica, R8 ila R"'in her biri bagimsiz olarak tercihen hidrojen, metil, metoksi veya sülfo'dur. Ayrica, Y4 ve Y5"in her biri bagimsiz olarak tercihen -CH=CH2 veya -CH2CH20803H'dir. Bu bulusun tercih edilen birinci çözümü olarak, Iacivertten siyaha reaktif boya bilesimi A bileseni ve B bileseninden olusur. Mevcut bulusun tercih edilen ikinci çözümü olarak, Iacivertten siyaha reaktif boya bilesimi ayrica C bilesenini içerir ve C bileseni formül (111) ila formül (IV) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen bir veya birkaçidir, bilesimdeki C bileseninin kütlesi, Ave B bilesenlerinin toplam kütlesinin %1 ila %50'si, tercihen %1 ila %40'i kadardir: SO3H (HI) R17 HO3S NH2 i-// SOZYQ R19 (IV) formül (III)'te: R12 ila R15'in her biri bagimsiz olarak H, C1 ila C4 alkil, C1 ila C4 alkoksi, karboksil veya sülfo, tercihen H, metil, metoksi, karboksil veya sülfo'dur; a 0 veya 1'dir; b 0 veya 1'dir; c ve d'nin her biri bagimsiz olarak 0 veya 1, tercihen 1'dir; D3 ve D4'ün her biri bagimsiz olarak ikame edilmis fenil, ikame edilmemis fenil, ikame edilmis naftil veya ikame edilmemis naftildir ve ikame edilmis fenil ve ikame edilmis naftilin ornatiklarinin sayisi sirasiyla 1 ve 3'tür ve ornatiklarin her biri bagimsiz olarak sunlardan olusan gruptan seçilir: amino, sülfo, üreido, C4 ila C4 alkanolamino, C4 ila C4 alkoksi ve hidroksil, tercihen ornatiklarin sayisi sirasiyla 1 ve 2'dir ve ornatiklarin her biri bagimsiz olarak amino, sülfo, üreido, asetilamino, metoksi ve hidroksilden olusan gruptan seçilir; formül (IV)'te: R16 ila R19'nin her biri bagimsiz olarak H, C1 ila C4 alkil, C1 ila C4 alkoksi veya sülfo, tercihen H, metil, metoksi veya sülfo'dur; e=0 ila 1'dir; Ayrica, bu bulusa uygun lacivertten siyaha reaktif boya bilesimi tercihen asagidaki bilesenleri A bileseni, bu, formül (I) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, bu, formül (II) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; ve C bileseni, bu, formül (III) ve/veya formül (IV) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir ve burada a ve b'nin her ikisi de 0'dir veya a ve b'den biri 0 digeri ise 1'dir, c1'dir ve d 0 veya 1'dir. Ayrica, lacivertten siyaha reaktif boya bilesimiA bileseni, B bileseni ve C bileseninden olusur. Ayrica, bu bulusa uygun lacivertten siyaha reaktif boya bilesimi tercihen asagidaki boya bilesenlerinden olusur: A bileseni, bu, formül (I) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, bu, formül (II) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; ve C bileseni, bu, formül (III) ve/veya formül (IV) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir ve burada a ve b'nin her ikisi de 0'dir veya a ve b'den biri 0 digeri ise 1'dir, c1'dir ve d 0 veya 1'dir. Mevcut bulusa uygun tercih edilen üçüncü çözüm olarak, boya bilesimi ayrica D bilesenini içerir, D bileseni formül (V) ila formül (VII) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen bir veya birkaçidir, bilesimdeki D bileseninin kütlesi, A ve B bilesenlerinin toplam kütlesinin %1 ila %50'si, tercihen %1 ila %40'i kadardir: H2N NH2 (R22)h (V) D5-N=N Alf/?kizi N N FSOJ" miRsi› Vw" \i / (R32)n formül (V)"te: f, g ve h'nin her biri bagimsiz olarak 0 ila 3 arasindan seçilir ve R20 , R21 ve R22'nin her biri bagimsiz olarak 01 ila C4 alkil, 01 ila C4 alkoksi veya sülfo, tercihen metil, metoksi veya sülfo'dur; Y10 ve Y""in her biri bagimsiz olarak -CH=CH2 , -C2H4OSOsH veya -C2H4Cl'dir; formül (VI)"da: D5 ve D6 'nin her biri bagimsiz olarak asagidaki formül (c), formül (d) veya formül (f)'nin bir (R25)- \ \(R28)i bagimsiz olarak H, C1 ila C4 alkil, C1 ila C4 aIkoksi veya sülfo, tercihen H, metil, metoksi ve sülfo'dur; i=0 ila 3"tür ve her bir R25 bagimsiz olarak sülfo, üreido ve C4 ila C4 aIkanoIamino'dan olusan gruptan seçilir, tercihen metil, sülfo, üreido veya asetiIamino'dur; j=0 ila 3"tür ve her bir R28 bagimsiz olarak hidroksil ve sülfo'dan olusan gruptan seçilir; tercihen -SOzY13'tür; formül (VII)"de: m=1 ila 3"tür ve her bir R31 bagimsiz olarak amino, sülfo, üreido, C1 ila C4 alkanolamino, C4 ila C4 aIkoksi ve hidroksilden olusan gruptan seçilir, tercihen amino, sülfo veya asetiIamino'dur; Y12-CH=CH2, -C2H4OSOsH veya -C2H4Cl'dir; n=0 ila 2"dir ve her bir R32 bagimsiz olarak lineer veya dallanmis C1 ila C4 alkil, C1 ila C4 aIkoksi veya sülfo, tercihen metil, metoksi veya sülfo'dur. Ayrica, D bileseni formül (VI) boya bilesigi ve bunun alkali metal tuzlarindan olusan gruptan seçilen en az biridir. Ayrica, lacivertten siyaha reaktif boya bilesimiA bileseni, B bileseni ve D bileseninden olusur. Ayrica, bu bulusa uygun lacivertten siyaha reaktif boya bilesimi tercihen asagidaki boya bilesenlerinden olusur: A bileseni, bu, formül (I) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, bu, formül (II) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; ve D bileseni, bu, formül (VI) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan Bu bulusa uygun tercih edilen dördüncü çözüm olarak, boya bilesimi ayrica C bileseni ve D bileseni içerir ve C bileseni formül (111) ila formül (IV) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen bir veya birkaçidir. Bilesimde C bileseninin kütlesi Ave B bilesenlerinin toplam kütlesinin %1 ila %50'si, tercihen %1 ila %40'idir; D bileseni formül (V) ila formül (VII) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen bir veya birkaçidir, bilesimdeki D bileseninin kütlesi, Ave B bilesenlerinin toplam kütlesinin %1 ila %50'si, tercihen %1 ila %40'i kadardir: Formül ('daki gruplar yukaridaki gibi tanimlanir. Ayrica, lacivertten siyaha reaktif boya bilesimi A bileseni, B bileseni, C bileseni ve D bileseninden olusur. Ayrica, C bileseni formül (III) ve/veya formül (IV) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir, burada a ve b'nin her ikisi de 0'dir veya a ve b'den biri 0 digeri ise 1'dir, c 1'dir ve d 0 veya 1'dir. Ayrica, D bileseni formül (VI) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan Ayrica, bu bulusa uygun lacivertten siyaha reaktif boya bilesimi tercihen asagidaki bilesenleri A bileseni, bu, formül (I) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, bu, formül (II) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; ve C bileseni, bu, formül (III) ve/veya formül (IV) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir ve burada a ve b'nin her ikisi de 0'dir veya a ve b'den biri 0 digeri ise 1'dir, c1'dir ve d 0 veya 1'dir. ve D bileseni, bu, formül (VI) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan Daha da ileri olarak, lacivertten siyaha reaktif boya bilesimi A bileseni, B bileseni, C bileseni ve D bileseninden olusur, burada A bileseni, formül (I) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, formül (II) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; C bileseni, formül (III) ve/veya formül (IV) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir ve burada a ve b'nin her ikisi de 0'dir veya a ve b'den biri 0 digeri ise 1'dir, c1'dir ve d 0 veya 1'dir. ve D bileseni, formül (VI) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir. Abileseni, B bileseni, C bileseni ve D bileseninin yani sira, bu bulusa uygun lacivertten siyaha reaktif boya bilesimi ayrica C.I. reaktif sari 145, C.I. reaktif kirmizi 194, C.I. reaktif kirmizi 195 ve C.I. reaktif kirmizi 198 gibi alisilmis bir veya birkaç gölge ayarlayici boya bileseni içerebilir ve alisilmis boya bilesenlerinin toplam miktari A bileseni, B bileseni, C bileseni ve D bileseninin toplam kütlesinin %30'undan fazla degildir. Özgün olarak, A bileseni tercihen asagidaki formül (I-1) ila formül ( I-66) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir: H3COCHN H2N NH2 (1-1) N=N NZNQSOZCHZCHZOSOSH H2NOCHN HzN NH2 SOZCHZCHZOSO3H ( I _2) 803" COOH N=N N=N4©ýSOZCH2CHZOSO3H H3CH2COCHN HZN NH2 SOZCHZCHZOSO3H ( I _3) H2N NH2 H2N NH2 SOZCHZCH20803H ( I _5) 803" COOH H2N NH2 SOZCHZCH20803H ( I _6) H3000HN N=N N= @SOZCHZCHZOSQH H2N NH2 SOZCHZCH20803H ( I _7) SOSH Hogs H3COCHN N= N=N SOZCHZCHZOSOSH H2N NH2 SOZCHZCH20803H ( I _8) SO3H Hoss H2N NH2 3 2 2 2 ( I _10) sogH COOH Hogs HOgSOHZCHZCOZS ( I _11) N=N N=N4©ýSOZCHZCHZOSOSH HSCOCHN HZN NH2 SOZCH20H20803H ( I _12) N=N NZNQSOZCHZCHZOSOSH SOZCH20H20803H ( I _13) Q 2 2 2 3 ( I _14) 303" COOH 2 2 2 3 ( I _15) SO3H COOH H3CO (1-16) SO3H C 0 OH H3CO QN-N N=N SOZCHZCHZOSO3H H3COCHN HZN NH2 3 2 2 2 ( I '18) 3 2 2 2 ( I _19) sogH COOH H3CO N=N N=N SOZCHZCHZOSO3H H2NOCHN HZN NH2 OCH3 SOZCHZCH20803H ( I _20) 3 COOH H3CO (1-21) so3H COOH H3co N= N= SOZCHZCHZOSO3H SOZCHZCHZOSO3H ( I _22) H2N NH2 SOgCH2CH20803H ( I _23) H3COCHN N= N= @SOZCHZCHzosoaH H2N NH2 SOZCHZCH20803H ( I _24) H2N NH2 2 2 2 3 ( I _25) H2N NH2 N=N N=N SOZCHZCH20803H H2NOCHN HZN NH2 SOZCH20H20803H ( I _27) N=N N=N SOZCHZCHZOSO3H chOCHN HZN NH2 SOZCHZCHZOSO3H ( I _28) H2N NH2 SOZCH2CH20803H ( I _29) SO3H COOH H3CO N=N N=N SOZCHZCH20803H H2N HzN NH2 SOZCH2CH20803H ( I _30) 3 COOH HO3S 2 NH2 SOZCHZCHZOSO3H SOZCH2CH20803H ( I _31) H3CH2C H2N NH2 SOZCH2CH20803H ( I _32) H2N NH2 OCH3 COOH Hogs HO3SH2C H2N NH2 H2N NH2 (1-35) Hoss N=N N=N SOZCHZCHZOSO3H H2N HZN NH2 SOZCHZCH20803H ( I _36) H2N N=N N=NQSOZCH2CH20803H H2N NH2 SOZCHZCHzosogH H2N N-N N-N HZN NH2 SOZCH2CH20803H (1-38) H3COCHN@N=N NN* H2N NH2 SOZCHZCHZOSO3H HOsSOH2CH2COZS ( I _39) H2N0CHN@N=N MN* H2N NH2 SOgCH20H20803H HO3SOH2CH2C028 ( I _40) HacOCHN@N=N N=N-\ H2N NH2 SOZCH2CHZOSOSH HO3SOH2CH2C028 ( I _41) HaCOCHNGîN N: WWE* SOzcHZCHZOSOSH HO3SOHZCH20028 3 COOH SOsH H2NOCHN N: mb] 303" COOH SOsH H3000HN SOgCH2CH2OSO3H HO3SOH2CH20028 ( I _44) SO3H COOH SOsH $03H COOH chOCHN N=N N: N 2 2 2 3 ( I -46) SOgCHZCH20803H $03H COOH H2NOCHN N=N =NN 2 2 2 3 ( I _47) H3COCHN@N= N=N4©ýSOZCH=CH2 H2N NH2 SO3H COOH HO3S H3COCHN N=N N=N 8020H=CH2 H2N NH2 SOZCHZCHZ ( I _49) H2NOCHN N=N N=N SOZCH=CH2 H2N NH2 CH3 803H COOH H300 H3COCHN N=N N=N 8020H=CH2 H2N NH2 HSCOCHN@N=N NNQ HZN NH2 SOZCH=CH2 SOZCH=CH2 ( I _52) SO3H COOH HOSS HZNOCHN H2N NH2 SO2CHZCH2 H3COCHN N=N N=N SO2CH=CH2 H2N NH2 SO2CH=CH2 ( 1 _54) HZNOCHN N=N N=N SO2CH=CH2 H2N NH2 803H COOH Hogs H2N Ni-i2 H2N NH2 SO3H SO3H H3COCHN N=N N=N H3000HNQN=N N=N CONHCHZCstOZCHZCHzosogH ( 1 _59) 803H COOH Hogs H3COCHN N=N N=N 303" COOH HZNOCHN N=N N=NQCONHCHZCHZSOZCHZCHzososH H2N NH2 H2N NH2 803" COOH H3COCHN HZN NHZ SOZCH2CH20803H ( I _63) HO3SOHZCHZCOZS SO3H COOH SOsH SOZCH20H20803H ( I _65) SO3H COOH OZNÖNzN N=NQSOzcH2CHZOSO3H H2N NH2 ( 1 -66) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir. Daha ileri olarak, A bileseni tercihen formül (1-1), formül (1-2), formül (1-4), formül (1-5), formül (1-6) ve formül (1-7) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir.. Özgün olarak, B bileseni tercihen asagidaki bilesikler ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir: H20=HCOZS@N=N*N=N4QISOZCH=CH2 HO3S SO3H HO3S SO3H HO3S 803H (H _4) 303" OH NH2 HO3S SOsH (II-5) HO3SOC 503" OH NH2 H038 803H 303" (II-10) HOgSOC2H4OZS4©ýN=N:":N=N4Q Ayrica, A bileseni tercihen formül (II-1) ve formül (ll-3) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir. Özgün olarak, C bileseni tercihen asagidaki bilesikler ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir: HO3SOC2H4028 NH2 HZC=H0028ÖN=N N=NQSOZCH=CH2 CH3 NH2 HossoczH4ozs~ÖýN=N N=NQSOZCH=CH2 HO3SOC2H4OZS@N=N N=N CH3 HO3SOC2H4O2S N=N N=N CH3 NH2 $03H $03H MHZ H3C N=N N=NQSOchH4OSO3H HOSSOCZH4OZS N=N N=NQCOOH H0330H2CH2C023 NH NQN O /N N\\ sogH HO3SOH2CH2CO2S N / N (III-13) H0350H20H2cozs N `N ûN//N ;ES/MN SOSH HO3SOH2CH2CO2S H0350H20H2cozs NH NsN SO3H HOgSOH20H2COZS N / H0380H2CH2C028 SOSH N `N H0380H2CH2C028 SOSH N \N HOgSOHZCH2COZS SOSH N \N HOgSOHzCHZCOZS 803H N \N SO3H (III-21) 3 2 2 2 3 NH2 N 3 2 2 2 NHCONH2 $03H N,/N N"N SO3H N ,/ N NsN H2N CCH3 3 2 2 2 NHCCCH3 803H ,N N" SO3H ,N N" H2N 0CH3 H0380H2CH2COZS SO3H ,N N" 3 2 2 2 NHCONH2 N"Nû/SO2CH20H20803H HOgSOHZCH2CO2S NsNû/SO2CH2CH20303H OCH3 NÇN NeN 3 2 2 2 NHCOCH3 N ç N HZHOss SOZCHZCH20803H 3 2 2 2 NHCONH2 N ç N SOZCHZCHzososH HO3SOC2H4028@N=N N=N O N=NQ H2N O 802C2H4OSO3H H2N O SOZCZH4OSO3H SO3H so3i-i O N=N N=N O N=NÜSOZCZH4OSO3H HO3SOCZH4OZS H2N O NH2 SO3H N=N N=N O N=N sogcgH4oso3H HO3SOC2H4OZS H2N O HOgSOCZH4OZS_®_N=N N=N O N=N`ÖISOZCzH40803H SOgH (III-47) H2N O OCH3 (HI-50) H2C=H2C028@N=N N=N O N=N`Q H2N Q $02CH2=CH2 HO3SOCZH4023@N=N Oc N SOZCZH4OSO3H N4©ýSOZC2H4OSO3H H0380C2H4028 N=N OC Hsc HO3S NH2 N SOZC2H4OSO3H HOgS (IV-3) HO3S NH2 N SOZCZH40803H NQSOZCH=CHZ H2C=HCOZS@N=N HOgS (IV -6) HZC=HCOZS N=N HO3SOC2H4OZS OH SOZC2H40803H (IV-8) HO3SOCZH4OZS@N=N @o HO3S NH2CH N SOZC2H40803H HO3SOC2H4O2S HOsS NHz N@502C2H4OSO3H N~©ýsozczH4oso3H Ayrica, C bileseni tercihen formül (DI-1) ila formül (DI-33) ve formül (IV-1) ila formül (IV-10) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir. Ayrica, Cbileseni tercihen formül (DI-1), formül (DI-2), formül (DI-4), formül (IV-1) ve formül (IV-3) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir. Özgün olarak, D bileseni asagidaki bilesikler ve bunlarin alkali metal tuzlarindan olusan û COOH ûseZCHZCHZOSOSH H2N NH2 SO2CH2CHZOSO3H (V-l) $02CH=CH2 (V_2) Ný :Ç: `N SOZCH2CH20803H SOSH /û/SOZCHZCHZOSOSH ûîsojCHH2CHzoSO3H (V_5) SO3H SOZCHZCH20803H SOZCH2CH20803H (V-6) 803H ûsozcmzwzososH SO2CH2CH20803H (V-7) SO3H OCH3 H2N NH2 SOZCH2CH20803H (V_8) H0380H2CH2C028 N=N CH3 HO OH N=N SOgCHgCHZOSO3H HOgSOHZCHZCOZS N=N N=N SOZCHZCHZOSO3H SO3H (VI-2) HO3SOH2CH2CO2S@N=N N4©~SO2CHZCH20503H HO3SOH2CH2COZS@N=N N SOZCHZCHZOSO3H 8% 0/14) Hosomcmcqs N=N N=N@SOZCH2CH20803H 3 2 2 2 HO OH HOSSOH2CHZCOZS@N=N SOzCHzCHzoSO3H (VI_7) 3 2 2 2 HO OH N SOßHßHgßow HOßomcmcms N=N N=N &%cmcmoahH HO3SOH20H20028 HO OH HOasOHZCHZCOZS N=N N=N SOZCHZCH20803H OCHS (VI-11) HossOHZOH20028@N=N N=N SOZCH20H20803H OCHs (VI-12) H2C=HC028 N=N N=N SOZCH=CH2 HO3SOCZH4OZS N=N CH3 HO OH N=N SOZCH=CH2 OCHS (VI-14) HZC=HCOZS N=N CH3 HO N=N SOZCH2CH20803H OCHS (VI-15) HZC=HCOZS4©IN=N N4©ýSOZCH=CH2 H2C=HCOZS HO OH SOZCH=CH2(VI_17) SOZCH=CH2 (VI-18) HO3SOHZCHZCOZS@N=N N SOZCH=CH2 H2C=HCOZS@N=N N=N SOZCH2CHZOSO3H 303" (VI-20) HO3SOHZCH2COZS@N=N HO3SOC2H4OZS N=N N=N SOZCZH4OSO3H OCHs (VI-22) HOSSOHZCHZCOZS N=N OCHs (VI-23) HOgSOHZCHZCOZS N=N N=N SOZCH=CH2 H20=HCOZS N=N N=N SOZCH=CH2 OCHs (VI-25) HossOC2H4OZSÜN=N HO3SOC2H4O2SQ-NzN N=NÂQ`N=N4©`SOZC2H4OSO3H H0380C2H4028 N=N N=N`QIN=N4©ISO2C2H4OSO3H HO3SOC2H4O2SQNzN N=NÂQ`N=N`QSOZC2H4OSO3H H0350C2H4025Qî HO3SOC2H4028 HO3SOC2H4028 N:N N=NÄQIN=N SO2CZH4OSO3H NHCONH2 (VL32) H0380C2H4OZS N:N CH3 HO N=NÄQIN=N SOZCZH40803H NHCOCH3 (VL3Q HOSSOCZH4OZSQN:: N=Nî©_N= NÂÖSOZCZHAiOSOgH (W 35) HO350C2H402S HO OH N=NÄQIN=N 802C2H40803H HO3SOC2H4OZSQN:N N=N4tN=N $02C2H4OSO3H HOSSOC2H4OZSQNzN N: NIN: N4©`802C2H4OSO3H HogsOC2H4OZSÜN=N N=NîN=N4®ýSOZC2H40803H 503" (VI-39) HO3SOCZH4OZSÜNzN N=N OC N=N SOZCZH4OSO3H 503" (VI-40) HO3SOCZH4OZS N= günü& H2NOCHN HO3SOCzH4028 N- OCHs (VI-42) chOCHN HO OH HO3SOC2H4O2S-QN=N O N:N H038002H4OZS N=N N:N HOgSOCZH4OZS N=N N:N HOgSOCzH4OZS`©*N4Q N- hh-NÄQISOZCZHAOSOEH 01149) HO3SOC2H4OZS_©_N:N O N=N N=N N=N4©ýsozczH4oso3H N=NÄ` 802C2 H4OSO3H HZC=HCOZSÜN= (VI-51) HO3SOC2H4OZSQ-î N=NÂQIN=N SOZCH=CH2 H2C=HCOZS@N:N N=NÂQ`N=N SOZCH=CH2 HOSSOC2H4OZSÜNzN N=N N=N SOchH4OSO3H HO3SOC2H4028QNzN NzNiçgHszN 802C2H4OSO3H HO3S ::NO (VII-1) HO3S N:N/û/ HZNIONHZ (VII-2) ûSOZCH2CH20803H Hogs` IHZNsN/û/ NHCOCH3 (VII-3) Ayrica, D bileseni tercihen formül (VI-1), formül (VI-3), formül (VI-4), formül (VI-26), formül (VI-54) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir.. Ayrica, D bileseni tercihen formül (VI-26), formül (VI-27), formül (VI-41) ve formül (VI-42) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir. Bu bulusa uygun boya bilesimi bilhassa tercihen A bileseni ve B bilesenini içerir, burada: bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir, daha da tercihen formül alkali metal tuzlarindan olusan gruptan seçilen en az biridir ve; B bileseni formül (ll-1) ve formül (ll-3) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; Ave B bilesenlerinin toplam kütlesine göre, A bileseninin kütle itibariyle orani %5 ila %50 ve B bileseninin kütle itibariyle orani %50 ila %95'tir. Bilhassa tercihen, bu bulusa uygun boya bilesimi A bileseni, B bileseni ve C bilesenini içerir, bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir, daha da tercihen formül bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, formül (11-1) ve formül (11-3) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir ve; bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; Ave B bilesenlerinin toplam kütlesine göre, A bileseninin kütle itibariyle orani %5 ila %50, B bileseninin kütle itibariyle orani %50 ila %95'tir ve C bileseninin kütlesi Ave B bilesenlerinin toplam kütlesinin %1 ila %50'sidir. Bilhassa tercihen, bu bulusa uygun boya bilesimi A bileseni, B bileseni ve D bilesenini içerir, A bileseni, formül (1-1) ila formül ( I -28) ve formül ( I -48) ila formül ( I -55) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir, daha da tercihen ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, formül (ll-1) ve formül (II-3) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; ve D bileseni tercihen formül (VI-26), formül (VI-27), formül (VI-41) ve formül (VI-42) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; Ave B bilesenlerinin toplam kütlesine göre, A bileseninin kütle itibariyle orani %5 ila %50, B bileseninin kütle itibariyle orani %50 ila %95'tir ve D bileseninin kütlesi Ave B bilesenlerinin toplam kütlesinin %1 ila %50'sidir. Bilhassa tercihen, bu bulusa uygun boya bilesimi A bileseni, B bileseni, C bileseni ve D bilesenini içerir, burada: A bileseni, formül (1-1) ila formül ( I -28) ve formül ( I -48) ila formül ( I -55) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir, daha da tercihen ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; B bileseni, formül (ll-1) ve formül (II-3) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; C bileseni formül (DI-1), formül (DI-2), formül (]]I-4), formül (IV-1) ve formül (IV-3) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; ve D bileseni formül (VI-26), formül (VI-27), formül (VI-41) ve formül (VI-42) boya bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; Ave B bilesenlerinin toplam kütlesine göre, A bileseninin kütle itibariyle orani %5 ila %50, B bileseninin kütle itibariyle orani %50 ila %95'tir, C bileseninin kütlesi A ve B bilesenlerinin toplam kütlesinin %1 ila %50'si ve D bileseninin kütlesi A ve B bilesenlerinin toplam kütlesinin %1 ila %50'sidir. Mevcut bulusa uygun lacivertten siyaha reaktif boya bilesiminde, kullanilan formül (11) ila formül (V1) boya bilesiklerinin tamami bilinen boyalardir ve alisilmis yöntemlerle sentezlenebilir, örnegin, teknikte uzman olanlar tarafindan iyi bilinen uygun bilesenler gerekli oranlarda kullanilarak alisilmis diazotizasyon ve birlestirme reaksiyonlari yoluyla hazirlanabilir. Formül (1) reaktif boya bilesigi örnegin reaktif boyalarda yaygin olarak kullanilan diazotizasyon ve birlestirme reaksiyonlari ile de hazirlanabilir: Formül (Ia) ila formül (Ic)'deki ornatiklar formül (I)'de tanimlananlarla aynidir. "2N{|\X1 HZN_k/_ J (1 )diazotizasyon reaksiyonu: Ihtiyaca göre, formül (Ia), formül (Ib) ve/ veya formül (Ic) bilesiklerinin her biri 1 saat ila 2 saat boyunca buzlu su ile çirpilir; çirpildiktan sonra belirli miktarda hidroklorik asit eklenir ve ardindan 20 dakika ila 30 dakika içinde bir sodyum nitrit çözeltisi eklenir, diazotizasyon arasinda (tercihen 0°C ile 20°C arasinda) kontrol edilerek gerçeklestirilir, reaksiyonun bitis noktasi 4-dimetilaminobenzaldehitin etanol çözeltisi ile tespit edilir (yani 5 saniye içinde renk degisimi olmazsa bitis noktasina ulasilmis demektir); diazotizasyondan sonra, fazla sodyum nitrit sülfamik asit ile elimine edilir ve formül (Ia), formül (Ib) ve/ veya formül (Ic) diazonyum çözeltisi elde edilir ve kullanim için depolanir; burada formül (Ia), formül (Ib) ve/ veya formül (Ic) bilesiklerinin her birinin hidroklorik asit ve sodyum nitrite göre molar orani 1: (1-3): (1-1,1), (2)birlestirme reaksiyonu: Ilk olarak, 3,5-diaminobenzoik asit su ile çözülür, çözeltinin pH'i 8.0 ile 12.0 arasinda olacak sekilde kontrol edilir ve çözeltinin sicakligi 15°C ile 25°C arasinda olacak sekilde kontrol edilir. Çözünmüs 3,5-diaminobenzoik asit çözeltisi yukaridaki (1). adimda hazirlanan formül (Ia) diazonyum çözeltisine eklenir. pH, sivi alkali veya sodyum bikarbonat ile 2.0 ila 6.0 arasinda olacak sekilde kontrol edilir, sicaklik 0°C ila 20°C arasinda olacak sekilde kontrol edilir ve birinci birlestirme reaksiyonu gerçeklestirilir, birinci reaksiyon çözeltisi H asit test çözeltisi ile test edilir, test parçasina boya bulasmamis ise, diazonyumun son noktaya kadar tamamen reaksiyona girdigi anlamina gelir, böylece 1. birlestirme ürünü elde edilir; ikinci olarak, (1). adimda hazirlanan formül (Ib) veya formül (Ic) diazonyum çözeltisi 1. birlestirme ürününe eklenir, pH sivi alkali veya sodyum bikarbonat ile 5,0 ile 8,0 arasinda olacak sekilde kontrol edilir, sicaklik 0°C ile 20°C arasinda olacak sekilde kontrol edilir ve ikinci birlestirme reaksiyonu gerçeklestirilir, ikinci reaksiyon çözeltisi H asit test çözeltisi ile test edilir, eger test parçasina boya bulasmamis ise, diazonyumun son noktaya kadar tamamen reaksiyona girdigi anlamina gelir, böylece 2. birlestirme ürünü elde edilir; üçüncü olarak, (1). adimda hazirlanan formül (Ib) veya formül (Ic) diazonyum çözeltisi 2. birlestirme ürününe eklenir, pH sivi alkali veya sodyum bikarbonat ile 5.0 ile 8 arasinda olacak10 sekilde kontrol edilir, sicaklik 0°C ile 20°C arasinda olacak sekilde kontrol edilir ve üçüncü birlestirme reaksiyonu gerçeklestirilir, üçüncü reaksiyon çözeltisi H asit test çözeltisi ile test edilir, test parçasina boya bulasmamis ise, diazonyumun son noktaya kadar tamamen reaksiyona girdigi anlamina gelir, böylece mevcut bulusa uygun formül (I) reaktif boya bilesigi Burada, her bir birlestirme reaksiyonunda, formül (Ia), formül (Ib) veya formül (Ic) bilesiginin Ayrica, eger hem D1 hem de D2 formül (a) veya formül (b) grubu ise, ikinci birlestirme reaksiyonu ve üçüncü birlestirme reaksiyonu tek bir birlestirme reaksiyonu olarak birlestirilebilir, yani (1). adimda hazirlanan formül (Ib) veya formül (Ic) diazonyum çözeltisi 1. birlestirme ürününe eklenir, sivi alkali veya sodyum bikarbonat ile pH 5,0 ile 8 arasinda olacak sekilde kontrol edilir, sicaklik 0°C ile 20°C arasinda olacak sekilde kontrol edilir ve ikinci birlestirme reaksiyonu gerçeklestirilir, ikinci reaksiyon çözeltisi H asit test çözeltisi ile test edilir, eger test parçasina boya bulasmamis ise, diazonyumun son noktaya kadar tamamen reaksiyona girdigi anlamina gelir, böylece formül (I) reaktif boya bilesigi elde edilir; burada, formül (Ib) veya formül (Ic) bilesiginin 3,5-diaminobenzoik aside göre molar orani (1 ,SJ-2,4): Mevcut bulusa uygun lacivertten siyaha reaktif boya bilesiminde, fenolik hidroksilin orto pozisyonunda baglanan boya bilesiklerinin, genellikle kararli bir kinohidrazon durumunda bulunduklari, yani genel formül (VI) boyalarinin esas itibariyle asagidaki formül (VIa) ve/veya formül (VIb) ve/veya formül (VIc) ve/veya formül (VId)'nin kinohidrazon yapisi içerdigi ve genel formül (II) ve formül (IV) boyalarinin sirasiyla esas itibariyle asagidaki formül (IIa) ve formül (IVa)"nin kinohidrazon yapisini içerdikleri vurgulanmalidir. Teknikte uzman kisilerin yazma aliskanliklari göz önünde bulundurularak, bulusun özetinde ve örneklerde azo-formu da yazili biçim olarak kullanilmistir, bu durum mevcut bulusun özünü etkilemez: 4 Ã:\IN_ N\ N :N4<:|: HO3 S 803 H R19(IVa) D5-N-N= \ D5-N=N Dö (VIa) D6 (VIb) D5-N=N D5-N-N: \ Yukaridaki formül (IIa) ve formül (IVa) ornatiklarinin tanimlari sirasiyla formül (II) ve formül (IV)"tekiler ile aynidir ve formül (VIa) ila formül (VId) ornatiklarinin tanimlari formül (VI),dakiler ile aynidir. Buna ek olarak, mevcut bulusa uygun lacivertten siyaha reaktif boya bilesiminde, A bileseni formül (I) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir, B bileseni formül (II) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir, C bileseni formül (111) ila formül (IV) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir ve D bileseni formül (V) ila formül (VII) bilesikleri ve bunlarin alkali metal tuzlarindan olusan gruptan seçilen en az biridir; bilesik alkali metal tuzu oldugunda, formül (1) ila formül (VII)"deki karboksil gruplari ve sülfonik asit gruplari, karboksilik asit veya sülfonik asidin alkali metal tuzu formunda bulunurlar. Tercihen, alkali metal tuzu sodyum tuzu veya potasyum tuzudur. Serbest asit formundaki boya bilesiklerinin ve (sodyum tuzu, potasyum tuzu vb. gibi) alkali metal tuzu formundaki boya bilesiklerinin ayni boyama niteliklerine sahip olduklari ve her bir tek renkli boya bilesiginin yapisal formülünün genellikle serbest asit formunda ifade edildigi meslek erbabi tarafindan bilinmektedir. Bununla birlikte, gerçek sentez sürecinde, bunlar genellikle (sodyum veya potasyum tuzu gibi) alkali metal tuzu formunda hazirlanir ve izole edilir ve ayrica meslek erbabi tarafindan iyi bilinen tuz formunda boyama için kullanilir. Mevcut bulusa uygun lacivertten siyaha reaktif boya bilesimini hazirlama yöntemi, boya bilesenlerinin söz konusu orana göre karistirilmasini içerir. Karistirma islemi, ögütücü, yogurma makinesi veya homojenlestirici gibi alisilmis mekanik araçlarla gerçeklestirilebilir. Karistirma isleminde, münferit boya bilesigi toz, granül, sulu bir çözelti veya sentetik bir çözelti seklinde mevcut olabilir. Münferit boya bilesigi sentetik çözelti seklinde karistirildiginda, mevcut bulusa uygun lacivertten siyaha reaktif boya bilesiminin sentetik çözeltiden ayrilmasi genel olarak bilinen bir yöntemle gerçeklestirilebilir, örnegin, boya tuzlanir ve (sodyum klorür veya potasyum klorür gibi) bir elektrolit tuzu ile bir reaksiyon ortamindan süzülür veya karisim buharlastirilir ve spreyle kurutulur. Dolayisiyla, boya bilesenleri ve bunlarin boya bilesimleri genellikle reaktif boyalarda yaygin olarak görülen (sodyum klorür, sodyum sülfat vb.) alisilmis elektrolit tuzunu (tuzlarini) içerir. Emtia olarak satildiginda veya dogrudan kullanildiginda, mevcut bulusa uygun lacivertten siyaha reaktif boya bilesimi yardimci madde içermeyebilir ve ayrica bir yardimci çözücü, bir dagitici, alkaliye dayanikli bir yardimci madde, birtoz geçirmez madde, bir yüzey aktif madde, birtampon ve bir hizlandirici gibi ticari boyalarda yaygin olarak kullanilan bir yardimci madde ile de eklenebilir. Bu nedenle, mevcut bulus ayni zamanda lacivertten siyaha reaktif boya bilesimini içeren lacivertten siyaha reaktif boya ürünü de saglamaktadir. Tercihen, lacivertten siyaha reaktif boya ürünü, lacivertten siyaha reaktif boya bilesimi ve bir yardimci madde içerir. Yardimci maddenin agirligi, lacivertten siyaha reaktif boya bilesiminin agirliginin %45'ini, tercihen %40'ini geçmez. Yardimci madde tercihen asagidaki bilesiklerden olusan gruptan seçilen bir veya birkaç bilesiktir: bir naftalin sülfonik asit/formaldehit kondensasyon ürünü (NNO), bir metilnaftalensülfonik asit/formaldehit kondensasyon ürünü (dispersan MF), bir difüzyon ajani CNF (benzilnaftalensülfonat/formaldehit kondensasyon ürünü), Yuanming tozu (endüstriyel sodyum sülfat), lignosülfonat, sodyum asetat, sodyum hidrojenkarbonat, sodyum sitrat, sodyum dihidrojen fosfat, disodyum hidrojen fosfat, kivam arttirici ve benzerleri. Tüm yardimci maddeler piyasada bulunan alisilmis ürünlerdir. Bu bulusa uygun lacivertten siyaha reaktif boya ürünü, selüloz elyaflarin, poliamid elyaflarin ve bunlarin kumaslarinin boyanmasi ve basilmasi için uygundur, bunlar azot içeren ve/veya hidroksil içeren elyaf malzemeleri olabilirler. Burada, selüloz elyaf tercihen pamuk elyaf veya rejenere elyaftir ve tabii ki kenevir elyaf gibi diger bitkisel elyaf veya bunlarin kumaslarini içerebilir; poliamid elyaf tercihen deri, yün veya ipek gibi hayvansal elyaf malzemeyi ve10 naylon 6 ve naylon 66 gibi sentetik elyaf malzemeyi içerir. Yukarida belirtilen elyaf malzeme, mevcut bulusa uygun lacivertten siyaha reaktif boya ürünü kullanilarak boyandiginda ve basildiginda, yaygin olarak kullanilan reaktif boya daldirma boyama yöntemi ve fular boyama yöntemi gibi bilinen reaktif boya boyama ve baski yöntemlerine göre gerçeklestirilebilir ve daldirma boyama yöntemi, kumasi kademeli olarak boyamak için bir kumasi bir boyama çözeltisine daldirma yöntemidir ve genellikle boyama, fiksaj, yikama, sabunlama, yikama, dehidrasyon, kurutma ve benzeri islemlerden geçmesi gerekir. Fular boyama yöntemi, kumasi önce bir boyama çözeltisine daldirma, ardindan kumasi bir rulodan geçirme, boyama çözeltisini kumasin iç kismina esit sekilde nüfuz ettirme ve ardindan kumasi buharlama, sicak çözündürme veya diger islemlerle isleme tabi tutma yöntemidir ve genellikle bir boya çözeltisi ile fularlama, kurutma (fiksaj çözeltisi ile fularlama), buharlama veya kürleme, yikama, sabunlama, yikama, kurutma vb. islemlerden geçmesi Genel olarak, kumaslarin boyali rengi için farkli gereksinimler nedeniyle, boyalarin kullanim miktari farklidir. Daldirma boyama ile boyandiginda, boyama derinligi (owf) genellikle %0.1 ile %10 arasindadir (bu, boyanin agirliginin kumasin agirliginin %0,1 ila %10'unu orani, agirlik itibariyle kumasin boyama çözeltisine orani olarak tanimlanir), baslangiç boyama sicakligi 30°C ila 60°C arasinda olacak sekilde kontrol edilir, boyama süresi 10 dakika ila 30 dakikadir, sabunlama sicakligi 85°C ila 95°C'dir, sabunlama süresi 10 dakika fikse pH'i 9 ila 11'dir. Fular boyama yöntemi ile boyandiginda, selüloz elyafinin boya çekme dakika ila 3 dakikadir. Fular yöntemlerinde soguk fular boyama yöntemi yaygin olarak kullanilir, bunda bir boya ve bir alkalin madde bir fular boyama makinesine verilir, bir rulo üzerine sarilir ve kaplanan rulo fiksaj için oda sicakliginda 2 saat ila 30 saat boyunca yavasça döndürülür ve ardindan iyice durulanir. Mevcut bulusun avantajlari, azot içeren ve/veya hidroksil içeren elyaf malzemenin boyanmasi ve basilmasi için kullanildiginda, mevcut bulusa uygun lacivertten siyaha reaktif boya bilesimi ve ürününün esas itibariyle iyi birikme, iyi uyumluluk, yüksek derecede fiksaj ve renk hasligi, bilhassa mükemmel yikama hasligi ve benzeri niteliklere sahip olmasinda somutlasmaktadir. Çizimlerin Kisa Açiklamasi Sekil 1, örnek 1'de elde edilen (I-1) bilesiginin kütle spektrumudur. Sekil 2 örnek 1'de elde edilen kromoforun (A) kütle spektrumudur.10 Özgün Düzenlemeler Mevcut bulus, özgün örneklerle baglantili olarak daha ayrintili olarak açiklanacaktir, ancak mevcut bulusun koruma kapsami bunlarla sinirli degildir: Bu bulusun örneklerinde kullanilan boya bilesikleri, 9erçek sentez isleminde sodyum tuzu formunda hazirlanir ve ayristirilir ve ayrica boyama için sodyum tuzu formunda kullanilir, ancak yazim kolayligi için, örneklerdeki boya bilesiklerinin tüm kimyasal formülleri serbest asit formunda ifade edilir ve önemli boyama nitelikleri sodyum tuzu formuna esdegerdir. (1) Diazotizasyon: yaklasik 1 saat boyunca çirpilir, hidroklorik asit ile eklenir ve ile eklenir. Diazotizasyon reaksiyonu, pH 0,5 ile 2,0 arasinda ve sicaklik T 0°C ile 20°C arasinda kontrol edilerek 1 ila 2 saat boyunca 9erçeklestirilir ve reaksiyonun bitis noktasi 4- dimetilaminobenzaldehitin etanol çözeltisi ile tespit edilir (yani, 5 saniye içinde renk degisimi olmazsa bitis noktasina ulasilir). Diazotizasyondan sonra, fazla sodyum nitrit sülfamik asit ile elimine edilir ve 4-(asetilamino)-2-amino-benzensülfonik asidin diazonyum çözeltisi elde edilir ve kullanim için saklanir. eklenir, yaklasik 1 saat boyunca çirpilir, %31 hidroklorik asit eklenir çözeltisi eklenir. Diazotizasyon reaksiyonu, pH 0,5 ile 2,0 arasinda ve sicaklik T 0°C ile 20°C arasinda kontrol edilerek 1 ila 2 saat boyunca 9erçeklestirilir ve reaksiyonun bitis noktasi 4- dimetilaminobenzaldehitin etanol çözeltisi ile tespit edilir (yani, 5 saniye içinde renk degisimi olmazsa bitis noktasina ulasilir). Diazotizasyondan sonra, fazla sodyum nitrit sülfamik asit ile elimine edilir ve para-esterin diazonyum çözeltisi elde edilir ve kullanim için saklanir. (2) Birlestirme reaksiyonu: 9,0 arasinda ve çözeltinin sicakligi 20°C ile 25°C arasinda olacak sekilde kontrol edilir. Çirpma isleminden sonra, (1). adimda elde edilen 0,1 mol 4-(asetilamino)-2-amino- benzensülfonik asit diazonyum çözeltisi 3,5-dihidroksibenzoik asit çözeltisine eklenir. pH, %30 sivi alkali ile 5 ila 5,5 arasinda olacak sekilde kontrol edilir, sicaklik 5°C ila 10°C arasinda olacak sekilde kontrol edilir, reaksiyon 0,5 ila 2 saat boyunca 9erçeklestirilir ve HPLC ile serbest 3,5-dihidroksibenzoik asit içeriginin %3'ün altinda oldugu tespit edildiginde,10 reaksiyon son noktaya ulasir ve böylece kütle spektrumu Sekil 2'de gösterilen asagidaki formülün (A) kromoforu elde edilir. H3COCHN H2N (A) (1). adimda elde edilen para-esterin diazonyum çözeltisi formül (A) kromoforuna eklenir, pH %30 sivi alkali ile 5 ila 5,5 arasinda olacak sekilde kontrol edilir ve sicaklik T 5°C ila 10°C arasinda olacak sekilde kontrol edilir, birlestirme reaksiyonu 0,5 saat ila 10 saat boyunca gerçeklestirilir. Reaksiyon çözeltisi H asit test çözeltisi ile test edilir, eger test parçasina boya bulasmamis ise, diazonyumun son noktaya kadartamamen reaksiyona girdigi anlamina gelir, böylece turuncu bir reaktif boya bilesigi (I-1) elde edilir, bunun Amax degeri suda 420 nm'dir. Ve bilesigin (I-1) kütle spektrumu Sekil 1'de gösterilir. SO3H COOH N=N N=N@sozcHzcHzoso3H H3COCHN H2N NH2 Örnek 2 ila 66: Örnek 1'de açiklanan azo boyanin hazirlama yöntemine atifta bulunarak, asagidaki tablo 1'de gösterilen yapida boya bilesikleri, sirasiyla, teknikte iyi bilinen ara maddelerin hammaddeleri kullanilarak asamali diazotizasyon ve birlestirme reaksiyonlari ile elde edilir. Örne Amax Reaktif boya bilesikleri kler (nm) N=N N=N4©ýSOZCHZCHZOSO3H SO3H COOH N=N N=NQSOZCH2CHZOSOSH H3CH2COCHN HZN NH2 H2N NH2 H2N NH2 H2N NH2 SO3H COOH H2N NH2 SO3H COOH HO3S H2N NH2 803H COOH HO3S H2N NH2 sogH COOH Hogs N 425 H0330H SO3H COOH HO3S 11 [ü] 425 H0330H N= N=NÜSOZCHZCHZOSOSH H3COCHN HZN NH2 12 [UI N=N N=NQSOZCH2CHZOSO3H 14 w 415 SOZCHZCHzososH (I 14) SO3H COOH [ü] 420 SO2CH2CHZOSO3H (I 15) sogH COOH H3CO 16 lü] 415 SO3H C 0 OH H3CO N=N N=N SOZCH2CH20803H H3COCHN HZN NH2 17 H 415 18 [|\|I 410 HOSSOHZCH2CO2S (I 18) 19 In] 410 HO3SOH2CH2COZS (I 19) 803H COOH H3CO N=N N=N SOZCH2CH20803H H2NOCHN HZN NH2 OCH3 N 415 3 COOH H3CO 21 N 415 (1-21 ) 3 COOH H3CO H2NOCHN HZN NH2 CH3 22 ll 415 H2N NH2 23 N 410 chOCHN N=N N=NQSOzcHzcHzososH H2N NH2 N 415 (1-25) H2N NH2 N=N N=N SOZCHZCH20803H 27 N 425 N=N N=N SOZCH20H20803H H3COCHN H2N NH2 28 N 425 503" COOH HZC=HCOCHN N=N N=NQSozcH20H20803H H2N NH2 3 COOH H3CO N=N N=N SO2CHZCH20803H H2N H2N NH2 ii 415 2 NH2 SO2CH2CH2OSO3H 31 w 410 SO2CH2CH2OSO3H (1_31) H3CH2C H2N NH2 32 'N 410 H2N NH2 H038H2C H2N NH2 34 [LI] 415 H2N NH2 3 5 IU] 4 10 HO3S N=N N=N SOZCHZCH20803H H2N HZN NH2 36 [UI 4 1 8 H2N N=N N=NQSOZCHZCH20803H H2N NH2 37 N 418 SOZCHZCHZOsogH (1-37) H2N N=N N=N H2N NH2 SOZCHZCHZOSO3H 3 8 H 418 I `SOZCHZCHZOSO3H (1-38) H2N NH2 SOZCHZCH20803H 39 435 HOgSOH2CH2COZS (1_39) HZNOCHN@N=N N=N .o H2N NH2 SOZCHZCH20803H 40 435 HO3SOHZCHZCOZS (1_40) H3COCHN@N=N Ni-i2 .E 'E `SOZCH2CH20803H CH3 COOH SO3H H3COCHN N=N N=N .o H2N NH2 SOZCHZCHZOSO3H 42 435 H0380H2CHZCOZS (1-42) 3 COOH SO3H H2NOCHN N=N N=N .o H2N NH2 SOZCHZCHZOsosH 43 435 HOgSOHzcHZCOZS (1_43) SO3H COOH SOsH HgCOCHN SOZCH20H20803H SO3H COOH SOsH SO3H COOH H3COCHN4ÖINHZN =NN N= N 46 435 . I SOZCHZCH20803H (1-46) SO2CH2CH2OSO3H H2NOCHNÖN=N N=N O H2N NH2 I I SOZCHZCH2OSOSH (1-47) H3COCHN@N=N N=NQSO2CH=CH2 H2N NH2 H2NOCHN N=N NINAQEIQCH: -CH2 50 H 418 SO3H COOH H300 H3COCHN N=N N=N 8020H=CH2 H2N NH2 51 N 418 HSCOCHN4®~N=N ?Q 2 SO2CH= CH2 52 'N' 415 H2NOCHN HZN SOZCH= CH2 53 TI' 425 H3COCHN N=N N=N SOZCH=CH2 H2N NH2 54 lu] 422 H2NOCHN N=N N=N SOZCH=CH2 H2N NH2 55 [UI 422 803H COOH Hogs HscOCHNÖN=N N=N4©ýNHCOCHZCHZSOZCHZCHZCI H2N NH2 56 [LI] 428 NHCOCHZCHZSOZCHZCHZCI (1-56) HWOCHNÖN-N N-NQNHCOCHZCHZSOZCHZCHzosoaH H2N NH2 57 [LI] SO3H SOsH chOCHN N=N N=N H2N NH2 CONHCHZCHZSOZCHZCHzosogH 59 T" 420 CONHCHZCHZSOZCHZCHzosogH (1_59) 60 'H' 430 803" COOH HZNOCHNÖN=N N=NQCONHCHZCHZSOZCHZCHZOsoaH H2N NH2 H2N NH2 303" COOH N=N N=N4©ýSOZCH=CH2 H3COCHN H2N NH2 HO3SOH2CH2COZS (1-64) 803H COOH 803H H2N SOZCH20H20803H chOCHN NH2 02N N=N N=NQSOZCHZCH20803H H2N NH2 olarak karistirilir ve elde edilen boya bilesimi ile pamuk alisilmis daldirma boyama ile siyaha boyanir ve bilhassa naylon ve yün üzerindeki boyamalarin yikama hasligi (ISO 105 C10- birikme ve fiksaj derecesi mükemmeldir. HZC=HCOZS@N=N:":N=N@SOZCH=CH2 HO3S SO3H ( ÖNN N=NQSOZCH2CHZOSOSH (1-1) 11-1) sodyum sülfat tozu mekanik olarak karistirilir ve elde edilen boya bilesimi ile pamuk alisilmis daldirma boyama ile siyaha boyanir, ve bilhassa naylon ve yün üzerindeki boyanin (ISO 105 /T2391-2014'e göre) birikme ve fiksaj derecesi mükemmeldir. N=N N=NQSOZCH2CHZOSOSH HOgSOC2H4OZSQ-NzN NHCONH2 (VI-26) Örnek 69: sodyum sülfat tozu mekanik olarak karistirilir ve elde edilen boya bilesimi ile pamuk alisilmis daldirma boyama ile koyu siyaha boyanir ve bilhassa naylon ve yün üzerindeki boyanin (ISO N=N N=NQSOZCH2CHZOSOSH HO38002H4OZS@N=N OC N49502C2H4OSO3H 21 pay formül (I-1) boyasi, 76 pay formül (II-3) boyasi, 1 pay formül (IV-1) boyasi, 2 pay formül (VI-26) boyasi, 10 pay sodyum sülfat tozu ve 10 pay dispersan MF mekanik olarak karistirilir ve elde edilen boya bilesimi ile pamuk koyu siyaha boyanir ve bilhassa naylon ve mükemmeldir. N=N N=NQSOZCH2CHZOSOSH SOZCH2CHZOSO3H (1_1) HO3SOCZH4OZS4©~N=N 00 N SOZCZH4OSO3H HOgSOC2H4OZSQNzN N=NÂQIN=N 802C2H4OSO3H NHCONH2 (VI-26) 17 pay formül (I-1) boyasi, 68 pay formül (II-3) boyasi, 7 pay formül (IV-1) boyasi, 8 pay formül (VI-26) boyasi, 10 pay sodyum sülfat tozu ve 10 pay dispersan MF mekanik olarak karistirilir ve elde edilen boya bilesimi ile pamuk koyu siyaha boyanir ve bilhassa naylon ve mükemmeldir. N=N N=NQSOZCH2CHZOSOSH SOZCH2CHZOSO3H (1_1 ) HO38002H4OZS4©~ N= N 00 N 80202H4OSO3H H0380C2H4OZSÜNzN NHCONH2 (VI-26) sodyum sülfat tozu ve 10 pay dispersan MF mekanik olarak karistirilir ve elde edilen boya bilesimi ile pamuk koyu siyaha boyanir ve bilhassa naylon ve yün üzerindeki boyanin (ISO GB / T2391-2014'e göre) birikme ve fiksaj derecesi mükemmeldir. 803" COOH ÖNE" N=NQSOZCH2CHZOSOSH H20=Hcozs4®ýN=N MQSOZCH= -CH2 HO3S SO3H (11 SO3H (111_1) Örnek 73 ila Örnek 224: Örnek 67 ila Örnek 72'den birinde açiklanan yönteme göre, Tablo 2'de listelenen oranlardaki boyalar mekanik olarak karistirilir ve elde edilen boya karisimi alisilmis reaktif boyama yöntemiyle pamuk lacivertten siyaha boyanir ve bilhassa naylon ve yün üzerindeki boyanin birikme ve fiksaj derecesi mükemmeldir. Örnek A Bileseni BileBseni C Bileseni Oran 73 (1-1) (II-3) _ 50:50 74 (1-1) (II-1) _ 45: 55 76 (1-4) (II-3) _ 35:65 77 (1-4) (II-1) _ 30:70 79 (I-6) (II-3) _ 25:75 80 (I-6) (II-1) _ 15:85 82 (1-2) (II-3) _ 5:95 83 (1-2) (II-1) _ 12:88 85 (1-5) (II-3) _ 24:76 86 (1-5) (II-1) _ 36:64 88 (1-7) (II-3) _ 38:62 89 (1-7) (II-1) _ 44:56 91 ( 20805 95 ( 45:55:25 (11-1)+(11- (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ : 95:10 :90:30 (111-2)+ _ _ (111-4)+ _ (111-2)+ :+ _ _ :75:15 :70:20 :+ _ _ 23:77: 20 32:68: 10 (111-17)+ _ _ (111-20)+ _ (111-22)+ _ _ (11-10) (18+18):64:(5+5) (1-66) 21:79; (10+10) (1-29) 27:73: (8+8) (1-30) :65: (7+7) (1-3 1)+(I- (11-12) (1-33) 45:55: (2+2+2) (1-34) 38:62: (5+5+5) (1-35) 34:66: (8+8+8) (15+15): 70: (6+6+6) (1-3 8) ; (40+40)= (10+10+10) (1-39) ; (40+45)= (15+15+15) (1-40) :80: (5+5+5+5) (1-41) (1-42) (1-43) :65: (5+5+5+5+5) (144) (11-11) 40:60: (5+5+5+5+5) (147) (11-12) 50:50: (4+4+4+4) (1-45) 45:55(5+5+5) (20+20): 60: (10+10+10) (1-50) (1-51) (1-52) (1-53) (1-56) (1-57) (1-58) (159) (11-11) :70:(7+7+7+7) (1-60) 38:62:(8+8+8+8) (1-61) 26:74:(6+6+6+6) (1-64) (1-65) 50:50:(3+3+3+3) (1-66) 48 :52 : (4+4+4+4) (1-55) 45:55:(5+5+5) (111-40)+ (111-30)+ (111-20)+ (111-1)+ (111-2)+ (111-4)+ 219 (1-54) 220 (1-53) içeren reaktif siyah boya hazirlanir: HO "satar-mio 5071115 N ün: N-Q-soz-iciiziz-osüaii Karsilastirma Örnegi 2: CN 1.730.566 A patentindeki Örnek 6'ya göre, asagidaki üç bilesenden olusan reaktif siyah boya hazirlanir: NaûgSOHZCH2COZSû sozciizciizosoawa N303SOH2CH2C02S N3038 NHZ 3035'& COOH Ö-N=N N=NQSOZCHZCHZOSOJNa Y2 Uygulama Örnegi 1: Örnek 67 ila Örnek 72'de (önceki teknige en yakin olan) ve karsilastirma Örnegi 1 ve karsilastirma Örnegi 2'de elde edilen kurutulmus reaktif siyah boyalar sirasiyla suda çözülür ve bir boyama çözeltisi hazirlamak için nihai konsantrasyon 50 g/L olacak sekilde sodyum sülfat tozu ile eklenir. Boyama konsantrasyonu (kumas agirligina göre boya) %4 olarak ayarlanir, banyo orani (kumasin gram cinsinden agirligi / boyama çözeltisinin mililitre cinsinden hacmi) 1:20 olarak ayarlanir, 30 dakika boyunca 60°C'de adsorpsiyon için pamuk banyoya koyulur, 45 dakika boyunca boya fiksaji için alkali (sodyum karbonat 209 / L) eklenir, boyanan kumas su ile yikanir, sabunlanir ve için kurutulur, böylece lacivertten siyaha boyali ve ISO 105 X12'deki yöntemlere göre gerçeklestirilir. Sonuçlar tablo 2'de görülür: Yikama hasligi Terleme direnci Surtunm e hasligi Örnekler Boyam a gücü Renk Pamuk Naylon Yün degisi Asit Alkali Kuru Islak mi boyama boyama boyama karsilastir karsilastir Uygulama Örnegi 2: Mevcut bulusun temsili örnekleri 67 ila 72 ve karsilastirma örnekleri 1 ve 2'de elde edilen reaktif boyalarin birikme niteligi GB/T 21875-2016 standardinda belirtilen bir yönteme göre test edilir ve örnekler 67 ila 72'nin reaktif boyalarinda birikmenin karsilastirma örnekleri 1 ve 2'den açikça daha iyi oldugu ve ayni boyama kosullari altinda boya miktarinin %5 ila %15 oraninda azaltilabilecegi ve bunun da dikkate deger bir ekonomik etki sagladigi görülmüstür. Uygulama Örnegi 3: Mevcut bulusun temsili örnekleri 67 ila 72 ve karsilastirma örnekleri 1 ila 2'de elde edilen reaktif boyalarin fiksaj derecesi GB/T2391-2014 standardinda belirtilen yönteme göre test edilir ve sonuçlar Tablo 3'te gösterilir: .. Örnek Örnek Örnek Örnek Örnek Örnek Karsilastirma Karsilastirma Ornekler .. " v' derecesi Özetle, mevcut bulusa uygun boyalar karsilastirma örneklerinden önemli ölçüde üstündür ve endüstri için haslik, birikme ve fiksaj derecesinde önemli gelisme saglarlar. TR TR DESCRIPTION DARK BLUE TO BLACK REACTIVE DYE COMPOSITION AND DYE PRODUCT THEREOF Technical Field The present invention relates to a reactive dye composition and dye product thereof, particularly a reactive dark blue-black dye composition and dye product thereof suitable for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials. It is related to. Background Technique Reactive black dye KNB has become the most widely used reactive black dye due to its low price, good fastnesses and easy washing. However, the substantivity of the dye to the fiber is low and the degree of dye absorption and fixation is not high. Aiming at the shortcomings of the reactive black dye KNB, dye researchers have carried out many studies on the research and development of reactive black dyes in recent years. In the actual application process, CN reactive black products still have problems such as poor deposition and poor washing fastness. Summary of the Invention To solve the above problems, the object of the present invention is a dark blue to black reactive dye composition having qualities such as good washing fastness, high degree of fixation and good deposition, suitable for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials and their blended fabrics and to provide paint products. To achieve the above objective, the present invention adopts a technical solution as follows: The present invention provides a dark blue to black reactive dye composition containing component A and component B; wherein component A is one or more selected from the group consisting of dye compounds of formula (I) and their alkali metal salts and component B is one or more selected from the group consisting of dye compounds of formula (II) and their alkali metal salts; According to component A and component B, the proportion of component A by mass is between 5% and 50%, and component B by mass is in Formula (I): D1 and Dz are each independently defined by the following formula (a) or formula (b). represented by a R 5 (a) C1 to C4 alkyl substituted with hydroxyl, sulfo or carboxyl, where R7 is C1 to C4 alkenyl, C2 to C4 alkenyl or -NH2; R3 is hydrogen, C1 to C4 alkyl, C1 to C4 alkoxy, carboxyl or sulfo; R4 to R6 are each independently hydrogen, C1 to C4 alkyl, C1 to C4 alkoxy or sulfo; X1 and R8 to R" are each independently hydrogen, C1 to C4 alkoxy, or sulfo; In the present invention, C1 to C4 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, may be tert-butyl, etc.; C1 to C4 alkoxy may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.; (b) Moreover, both D1 and D2 are preferably the group of formula (a). Furthermore, R1 and R2 are each independently preferably hydrogen or -COR7, wherein R7 is also methyl or -NH2. , R 3 is preferably hydrogen, methyl, methoxy, carboxyl or sulfo. Further, R 4 to R 6 are each independently preferably hydrogen, methyl, methoxy or sulfo. Further, X 1 and X 2 are each independently preferably -. SOzY1 is -NHCOCH2CH2802Y2 or -CONHCH2CH2802Y3 where Y1 to Y3 are each independently -CH=CH2 or -CH2CH20803H. Further, R8 to R" are each independently preferably hydrogen, methyl, methoxy or sulfo. Furthermore, Y4 and Y5" are each independently preferably -CH=CH2 or -CH2CH20803H. In the first preferred solution of this invention, the dark blue to black reactive dye composition consists of component A and component B. As a second preferred solution of the present invention, the dark blue to black reactive dye composition further contains component C, which component C is one or more selected from the group consisting of compounds of formula (111) to formula (IV) and alkali metal salts thereof, the mass of component C in the composition being greater than that of the components A and B. 1 to 50%, preferably 1 to 40% of the total mass of: SO3H (HI) R17 HO3S NH2 i-// SOZYQ R19 (IV) in formula (III): R12 to R15 each is independently H, C1 to C4 alkyl, C1 to C4 alkoxy, carboxyl or sulfo, preferably H, methyl, methoxy, carboxyl or sulfo; a is 0 or 1; b is 0 or 1; c and d are each independently 0 or 1, preferably 1; D3 and D4 are each independently substituted phenyl, unsubstituted phenyl, substituted naphthyl, or unsubstituted naphthyl, and the number of substituents of substituted phenyl and substituted naphthyl is 1 and 3, respectively, and each of the substituents is independently selected from the group consisting of : amino, sulfo, ureido, C4 to C4 alkanolamino, C4 to C4 alkoxy and hydroxyl, preferably the number of substituents is 1 and 2, respectively, and each of the substituents is independently selected from the group consisting of amino, sulfo, ureido, acetylamino, methoxy and hydroxyl; in formula (IV): R16 to R19 are each independently H, C1 to C4 alkyl, C1 to C4 alkoxy or sulfo, preferably H, methyl, methoxy or sulfo; e=0 to 1; Furthermore, the dark blue to black reactive dye composition according to the present invention preferably comprises component A, at least one of which is selected from the group consisting of dye compounds of formula (I) and alkali metal salts thereof; Component B is at least one selected from the group consisting of dye compounds of formula (II) and their alkali metal salts; and component C, which is at least one selected from the group consisting of dye compounds of formula (III) and/or formula (IV) and alkali metal salts thereof, wherein a and b are both 0 or one of a and b 0 and the other is 1, c is 1 and d is 0 or 1. Moreover, the dark blue to black reactive dye composition consists of component A, component B and component C. Furthermore, the dark blue to black reactive dye composition according to the present invention preferably comprises the following dye components: component A, which is at least one selected from the group consisting of dye compounds of formula (I) and alkali metal salts thereof; Component B is at least one selected from the group consisting of dye compounds of formula (II) and their alkali metal salts; and component C, which is at least one selected from the group consisting of dye compounds of formula (III) and/or formula (IV) and alkali metal salts thereof, wherein a and b are both 0 or one of a and b 0 and the other is 1, c is 1 and d is 0 or 1. As a third preferred solution according to the present invention, the dye composition further comprises component D, which is one or more selected from the group consisting of dye compounds of formula (V) to formula (VII) and their alkali metal salts, the mass of component D in the composition being that of components A and B. 1 to 50%, preferably 1 to 40% of the total mass: H2N NH2 (R22)h (V) D5-N=N Alf/? daughter N 01 to C4 alkyl, 01 to C4 alkoxy or sulfo, preferably methyl, methoxy or sulfo; Y10 and Y" are each independently -CH=CH2, -C2H4OSOsH or -C2H4Cl in formula (VI); D5 and D6 are each independently a (R25)-\\(R28) of formula (c), formula (d) or formula (f) independently H, C1 to C4 alkyl, C1 to C4 alkoxy or sulfo, preferably H, methyl, methoxy and sulfo; i=0 to 3" and each R25 is independently selected from the group consisting of sulfo, ureido and C4 to C4 alkanolamino, preferably methyl, sulfo, ureido or acetylamino; j=0 to 3" and each R28 is independently selected is selected from the group consisting of hydroxyl and sulfo; preferably -SO2Y13; In formula (VII): m=1 to 3 and each R31 is independently selected from the group consisting of amino, sulfo, ureido, C1 to C4 alkanolamino, C4 to C4 alkoxy and hydroxyl, preferably amino, sulfo or acetylamino; Y12 is -CH=CH2, -C2H4OSOsH or -C2H4Cl; n=0 to 2" and each R 32 is independently linear or branched C 1 to C 4 alkyl, C 1 to C 4 alkoxy or sulfo, preferably methyl, methoxy or sulfo. Additionally, component D is the dye compound of formula (VI) and its alkali At least one selected from the group consisting of metal salts. Furthermore, the dark blue to black reactive dye composition consists of component A, component B and component D. Moreover, the dark blue to black reactive dye composition according to the present invention preferably consists of the following dye components: Component A, which is of formula (I). component B, which is at least one selected from the group consisting of dye compounds of formula (II) and their alkali metal salts; and component D, which is at least one selected from the group consisting of dye compounds of formula (II) and their alkali metal salts; As a fourth preferred solution according to the present invention, the dye composition further comprises component C and component D, wherein component C is one or more selected from the group consisting of compounds of formula (111) to formula (IV) and alkali metal salts thereof. The mass of component C in the composition is 1 to 50%, preferably 1 to 40%, of the total mass of components A and B; Component D is one or more selected from the group consisting of dye compounds of formula (V) to formula (VII) and alkali metal salts thereof, the mass of component D in the composition being from 1 to 50%, preferably from 1 to 40%, of the total mass of the A and B components. The groups in formula () are defined as above. Furthermore, the dark blue to black reactive dye composition consists of component A, component B, component C and component D. Additionally, component C consists of dye compounds of formula (III) and/or formula (IV) and at least one selected from the group consisting of alkali metal salts wherein a and b are both 0 or one of a and b is 0 and the other is 1, c is 1, and d is also 0 or 1. Component D, consisting of dye compounds of formula (VI) and their alkali metal salts. Furthermore, the dark blue to black reactive dye composition according to the present invention preferably contains components A, which is at least one selected from the group consisting of dye compounds of formula (I) and their alkali metal salts. component B, which is at least one selected from the group consisting of dye compounds of formula (II) and alkali metal salts thereof; and component C, which is at least one selected from the group consisting of dye compounds of formula (III) and/or formula (IV) and alkali metal salts thereof, wherein a and b are both 0 or one of a and b 0 and the other is 1, c is 1 and d is 0 or 1. and component D, which is composed of dye compounds of formula (VI) and their alkali metal salts. Further, the dark blue to black reactive dye composition consists of component A, component B, component C and component D, wherein component A is the dye of formula (I). is at least one selected from the group consisting of compounds and alkali metal salts thereof; Component B is at least one selected from the group consisting of dye compounds of formula (II) and their alkali metal salts; Component C is at least one selected from the group consisting of dye compounds of formula (III) and/or formula (IV) and alkali metal salts thereof, wherein a and b are both 0 or one of a and b is 0 and the other is 0. is 1, c is 1, and d is 0 or 1. and component D is at least one selected from the group consisting of dye compounds of formula (VI) and alkali metal salts thereof. Besides component A, component B, component C and component D, the dark blue to black reactive dye composition according to the present invention is also C.I. reactive yellow 145, C.I. reactive red 194, C.I. reactive red 195 and C.I. It may contain one or more conventional shade adjusting dye components, such as reactive red 198, and the total amount of the conventional dye components is not more than 30% of the total mass of component A, component B, component C and component D. Specifically, component A is preferably at least one selected from the group consisting of the following dye compounds of formula (I-1) to formula (I-66) and their alkali metal salts: H3COCHN H2N NH2 (1-1) N=N NZNQSOZCHZCHZOSOSH H2NOCHN HzN NH2 SOZCHZCHZOSO3H ( I _2) 803" COOH N=N N=N4©SOZCH2CHZOSO3H H3CH2COCHN HZN NH2 SOZCHZCHZOSO3H ( I _3) H2N NH2 H2N NH2 SOZCHZCH20803H ( I _5) 803" COOH H2N NH2 SOZCHZCH20803H ( I _6) HN N=N N= @SOZCHZCHZOSQH H2N NH2 SOZCHZCH20803H ( I _7) SOSH Hogs H3COCHN N= N=N SOZCHZCHZOSOSH H2N NH2 SOZCHZCH20803H ( I _8) SO3H Hoss H2N NH2 3 2 2 2 ( I _10) sogH COOH Hogs HOgSOHZCHZCOZS ( I _11) N=N N=N4©ý SOZCHZCHZOSOSH HSCOCHN HZN NH2 SOZCH20H20803H ( I _12) N=N NZNQSOZCHZCHZOSOSH SOZCH20H20803H ( I _13) Q 2 2 2 3 ( I _14) 303" COOH 2 2 2 3 ( I _15) SO3H COOH H3CO (1-16) SO3H C 0 OH H3CO QN- N N=N SOZCHZCHZOSO3H H3COCHN HZN NH2 3 2 2 2 ( I '18) 3 2 2 2 ( I _19) sogH COOH H3CO N=N N=N SOZCHZCHZOSO3H H2NOCHN HZN NH2 OCH3 SOZCHZCH20803H ( I _20) 3 COOH H3CO (1-21) ) so3H COOH H3co N= N= SOZCHZCHZOSO3H SOZCHZCHZOSO3H ( I _22) H2N NH2 SOgCH2CH20803H ( I _23) H3COCHN N= N= @SOZCHZCHzosoaH H2N NH2 SOZCHZCH20803H ( I _24) H2N NH2 2 2 2 3 ( I _ 25) H2N NH2 N=N N =N SOZCHZCH20803H H2NOCHN HZN NH2 SOZCH20H20803H ( I _27) N = N ZCHZCH20803H H2N HzN NH2 SOZCH2CH20803H ( I _30) 3 COOH HO3S 2 NH2 SOZCHZCHZOSO3H SOZCH2CH20803H ( I _31) H3CH2C H2N NH2 SOZCH2CH20803H ( I _32) H2N NH2 OCH3 COOH Hogs HO3SH2C H2N NH2 H2N NH2 (1-35) Hoss N=N N=N SOZCHZCHZOSO3H H2N HZN NH2 SOZCHZCH20803H ( I _36) H2N N =n 2 SOgCH20H20803H HO3SOH2CH2C028 ( I _40) HacOCHN@ N=N N=N-\ H2N NH2 SOZCH2CHZOSOSH HO3SOH2CH2C028 ( I _41) HaCOCHNGîN N: WWE* SOzcHZCHZOSOSH HO3SOHZCH20028 3 COOH SOsH H2NOCHN N: mb] 303" COOH SOsH H3000HN SOgCH2CH2OSO3H HO3SOH2CH2 0028 ( I _44) SO3H COOH SOsH $03H COOH chOCHN N= N N: N 2 2 2 3 ( I -46) SOgCHZCH20803H $03H COOH H2NOCHN N=N =NN 2 2 2 3 ( I _47) H3COCHN@N= N=N4©ýSOZCH=CH2 H2N NH2 SO3H COOH HO3S H3COCHN N=N N =N 8020H=CH2 H2N NH2 SOZCHZCHZ ( I _49) H2NOCHN N=N N=N SOZCH=CH2 H2N NH2 CH3 803H COOH H300 H3COCHN N=N N=N 8020H=CH2 H2N NH2 HSCOCHN@N=N NNQ HZN NH2 SOZCH=CH2 SOZCH =CH2 ( I _52) SO3H COOH HOSS HZNOCHN H2N NH2 SO2CHZCH2 H3COCHN N=N N=N SO2CH=CH2 H2N NH2 SO2CH=CH2 ( 1 _54) HZNOCHN N=N N=N SO2CH=CH2 H2N NH2 803H COOH Hogs H2N Ni-i2 H2N NH2 SO3H SO3H H3COCHN N=N N=N H3000HNQN=N N=N CONHCHZCstOZCHZCHzosogH ( 1 _59) 803H COOH Hogs H3COCHN N=N N=N 303" COOH HZNOCHN N=N N=NQCONHCHZCHZSOZCHZCHzososH H2N NH2 H2N NH2 80 3" COOH H3COCHN HZN NHZ SOZCH2CH20803H ( I _63) HO3SOHZCHZCOZS SO3H COOH SOsH SOZCH20H20803H ( I _65) SO3H COOH OZNÖNzN N=NQSOzcH2CHZOSO3H H2N NH2 ( 1 -66) It is at least one selected from the group consisting of compounds and their alkali metal salts. Further, component A is preferably present in compounds of formula (1-1), formula (1-2), formula (1-4), formula (1-5), formula (1-6) and formula (1-7) and Specifically, component B is preferably at least one selected from the group consisting of the following compounds and their alkali metal salts: H20=HCOZS@N=N*N=N4QISOZCH=CH2 HO3S SO3H HO3S SO3H HO3S 803H (H _4) 303" OH NH2 HO3S SOsH (II-5) HO3SOC 503" OH NH2 H038 803H 303" (II-10) HOgSOC2H4OZS4©ýN=N:":N=N4Q Furthermore, component A is preferably of the formula (II- 1) and compounds of formula (II-3) and their alkali metal salts. Specifically, component C is preferably at least one selected from the group consisting of the following compounds and their alkali metal salts: HO3SOC2H4028 NH2 HZC=H0028ÖN=N N=NQSOZCH=CH2 CH3 NH2 HossoczH4ozs~ÖýN=N N=NQSOZCH=CH2 HO3SOC2H4OZS@N=N N=N CH3 HO3SOC2H4O2S N=N N=N CH3 NH2 $03H $03H MHZ H3C N=N N=NQSOchH4OSO3H HOSSOCZH4OZS N=N N=NQCOOH H0330H2CH2C023 NH NQN O /N N\\ sogH HO3SOH2CH2CO2S N / N (III-13) H0350H20H2co zs N `N ûN// N ;ES/MN SOSH HO3SOH2CH2CO2S H0350H20H2cozs NH NsN SO3H HOgSOH20H2COZS N / H0380H2CH2C028 SOSH N `N H0380H2CH2C028 SOSH N \N HOgSOHZCH2COZS SOSH N \N HOgSOHzCHZCOZS 803H N \N SO3H (III-21) 3 2 2 2 3 NH2 N 3 2 2 2 NHCONH2 $03H N,/N N"N SO3H N ,/ N NsN H2N CCH3 3 2 2 2 NHCCCH3 803H ,N N" SO3H ,N N" H2N 0CH3 H0380H2CH2COZS SO3H ,N N" 3 2 2 2 NHCONH2 N"Nû/SO2CH20H20803H HOg SOHZCH2CO2S NsNû/ SO2CH2CH20303N O3H SO3H so3i-i O N=N N=N O N=NÜSOZCZH4OSO3H HO3SOCZH4OZS H2N O NH2 SO3H N=N N=N O N=N sogcgH4oso3H HO3SOC2H4OZS H2N O HOgSOCZH4OZS_®_N=N N=N O N=N`ÖISOZCzH40803H SOgH (III-47) H2N O OCH3 (HI-50) H2C=H2C028@N=N N=N O N= N`Q H2N Q $02CH2=CH2 HO3SOCZH4023@N=N Oc N SOZCZH4OSO3H N4©ýSOZC2H4OSO3H H0380C2H4028 N=N OC Hsc HO3S NH2 N SOZC2H4OSO3H HOgS (IV-3) HO3S NH2 N SOZCZH40803H NQSOZ CH=CHZ H2C=HCOZS@N=N HOgS (IV -6) HZC=HCOZS N=N HO3SOC2H4OZS OH SOZC2H40803H (IV-8) HO3SOCZH4OZS@N=N @o HO3S NH2CH N SOZC2H40803H HO3SOC2H4O2S HOsS NHz N@502C2H4OSO3H N~©ýsozczH4oso 3H Additionally, component C is preferably formed by the formula (DI- 1) is at least one selected from the group consisting of compounds of formula (DI-33) and compounds of formula (IV-1) to formula (IV-10) and their alkali metal salts. Furthermore, component C is preferably at least one selected from the group consisting of compounds of formula (DI-1), formula (DI-2), formula (DI-4), formula (IV-1) and formula (IV-3) and their alkali metal salts. . Originally, the D component consists of the following compounds and their alkali metal salts: û COOH ûseZCHZCHZOSOSH H2N NH2 SO2CH2CHZOSO3H (V-l) $02CH=CH2 (V_2) SO3H (V_5) SO3H SOZCHZCH20803H SOZCH2CH20803H (V -6) 803H ûsozcmzwzososH SO2CH2CH20803H (V-7) SO3H OCH3 H2N NH2 SOZCH2CH20803H (V_8) H0380H2CH2C028 N=N CH3 HO OH N=N SOgCHgCHZOSO3H HOgSOHZCHZCOZS N=N N=N SOZCHZCHZOSO3H SO3H (VI-2) HO3SOH2CH2CO2S@N=N N4© ~SO2CHZCH20503H HO3SOH2CH2COZS@N=N N SOZCHZCHZOSO3H 8% 0/14) Hosomcmcqs N=N N=N@SOZCH2CH20803H 3 2 2 2 HO OH HOSSOH2CHZCOZS@N=N SOzCHzCHzoSO3H (VI_7) 3 2 2 2 HO OH N SOß HßHgßow HOßomcmcms N=N N= N &%cmcmoahH HO3SOH20H20028 HO OH HOasOHZCHZCOZS N=N N=N SOZCHZCH20803H OCHS (VI-11) HossOHZOH20028@N=N N=N SOZCH20H20803H OCHs (VI-12) H2C=HC028 N=N N=N SOZCH=CH2 HO3SOCZH 4OZS N=N CH3 HO OH N=N SOZCH=CH2 OCHS (VI-14) HZC=HCOZS N=N CH3 HO N=N SOZCH2CH20803H OCHS (VI-15) HZC=HCOZS4©IN=N N4©ýSOZCH=CH2 H2C=HCOZS HO OH SOZCH =CH2(VI_17) SOZCH=CH2 (VI-18) HO3SOHZCHZCOZS@N=N N SOZCH=CH2 H2C=HCOZS@N=N N=N SOZCH2CHZOSO3H 303" (VI-20) HO3SOHZCH2COZS@N=N HO3SOC2H4OZS N=N N=N SOZCZH4OSO3H OCHs (VI-22) HOSSOHZCHZCOZS N=N OCHs (VI-23) HOgSOHZCHZCOZS N=N N=N SOZCH=CH2 H20=HCOZS N=N N=N SOZCH=CH2 OCHs (VI-25) HossOC2H4OZSÜN=N HO3SOC2H4O2SQ-NzN N= NÂQ'N=N4©`SOZC2H4OSO3H H0380C2H4028 N=N N=N`QIN=N4©ISO2C2H4OSO3H HO3SOC2H4O2SQNzN OC2H4028 N:N N=NÄQIN=N SO2CZH4OSO3H NHCONH2 (VL32) H0380C2H4OZS N:N CH3 HO N=NÄQIN=N SOZCZH40803H NHCOCH3 (VL3Q HOSSOCZH4OZSQN:: N=Nî©_N= NÂÖSOZCZHAiOSOgH (W 35) HO350C2H402S HO OH N=NÄQIN=N 802C2H40803H HO3SOC2H4OZSQN:N N=N4tN=N $02C2H4OSO3H HOSSOC2H4OZSQNzN N: NIN: N4©` 802C2H4OSO3H HogsOC2H4OZSÜN=N N=NîN=N4®ýSOZC2H40803H 503" (VI-39) HO3SOCZH4OZSÜnzN N=N OC N=N SOZCZH4OSO3H 503" (VI-40) HO3SOCZH4OZS zH4028 N-OCHs (VI-42) chOCHN HO OH HO3SOC2H4O2S-QN=N O N:N H038002H4OZS N=N N:N HOgSOCZH4OZS N=N N:N HOgSOCzH4OZS`©*N4Q N- hh-NÄQISOZCZHAOSOEH 01149) HO3SOC2H4OZS_©_N:N O N=N N=N N=N 4©ýsozczH4oso3H N=NÄ` 802C2 H4OSO3H HZC=HCOZSÜN= (VI-51) HO3SOC2H4OZSQ-î N=NÂQIN=N SOZCH=CH2 H2C=HCOZS@N:N N=NÂQ`N=N SOZCH=CH2 HOSSOC2H4OZSÜNzN N=N N=N SOchH4OSO3H HO3SOC2H4028QNzN NzNiçgHszN 802C2H4OSO3H HO3S ::NO (VII-1) HO3S N:N/û/ HZNIONHZ (VII-2) ûSOZCH2CH20803H Hogs` IHZNsN/û/ NHCOCH3 (VII-3) Moreover, component D is preferably formed by formula (VI-1), formula (VI-3), is at least one selected from the group consisting of compounds of formula (VI-4), formula (VI-26), formula (VI-54) and their alkali metal salts. Furthermore, component D is preferably selected from the group consisting of compounds of formula (VI-26), formula (VI-54). 27) is at least one selected from the group consisting of compounds of formula (VI-41) and formula (VI-42) and their alkali metal salts. The dye composition according to the present invention particularly preferably comprises component A and component B, wherein: at least one selected from the group consisting of alkali metal salts thereof, more preferably at least one selected from the group consisting of alkali metal salts of the formula and; Component B is at least one selected from the group consisting of dye compounds of formula (II-1) and formula (II-3) and their alkali metal salts; Based on the total mass of components A and B, the fraction by mass of component A is 5 to 50% and the fraction by mass of component B is 50 to 95%. Particularly preferably, the dye composition according to the present invention comprises component A, component B and component C, at least one selected from the group consisting of alkali metal salts thereof, more preferably at least one selected from the group consisting of alkali metal salts thereof; Component B is at least one selected from the group consisting of dye compounds of formula (11-1) and formula (11-3) and their alkali metal salts; is at least one selected from the group consisting of compounds and alkali metal salts thereof; Based on the total mass of Ave B components, the mass fraction of component A is 5% to 50%, the mass fraction of component B is 50% to 95%, and the mass of component C is 1% to 50% of the total mass of Ave B components. Particularly preferably, the dye composition according to the present invention contains component A, component B and component D, component A, dye compounds of formula (I-1) to formula (I-28) and formula (I-48) to formula (I-55). and at least one selected from the group consisting of alkali metal salts thereof, more preferably at least one selected from the group consisting of alkali metal salts thereof; Component B is at least one selected from the group consisting of dye compounds of formula (II-1) and formula (II-3) and their alkali metal salts; and component D is preferably at least one selected from the group consisting of compounds of formula (VI-26), formula (VI-27), formula (VI-41) and formula (VI-42) and alkali metal salts thereof; Based on the total mass of Ave B components, the mass fraction of component A is 5% to 50%, the mass fraction of component B is 50% to 95%, and the mass of component D is 1% to 50% of the total mass of Ave B components. Particularly preferably, the dye composition according to the present invention contains component A, component B, component C and component D, wherein: component A, formula (1-1) to formula (I-28) and formula (I-48) to formula (I). -55) is at least one selected from the group consisting of dye compounds and alkali metal salts thereof, more preferably at least one selected from the group consisting of alkali metal salts thereof; Component B is at least one selected from the group consisting of dye compounds of formula (II-1) and formula (II-3) and their alkali metal salts; Component C is at least one selected from the group consisting of dye compounds of formula (DI-1), formula (DI-2), formula (]]I-4), formula (IV-1) and formula (IV-3) and their alkali metal salts. is one; and component D is at least one selected from the group consisting of dye compounds of formula (VI-26), formula (VI-27), formula (VI-41) and formula (VI-42) and alkali metal salts thereof; Based on the total mass of components A and B, the mass of component A is 5% to 50%, the mass of component B is 50% to 95%, the mass of component C is 1% to 50% of the total mass of components A and B, and the mass of component D is 5% to 95% of the total mass of components A and B. Its mass is 1% to 50% of the total mass of components A and B. In the dark blue to black reactive dye composition according to the present invention, all of the dye compounds of formula (11) to formula (V1) used are known dyes and can be synthesized by conventional methods, for example, they can be prepared by conventional diazotization and coupling reactions using suitable components well known to those skilled in the art in the required proportions. The reactive dye compound of formula (1) can also be prepared, for example, by diazotization and coupling reactions commonly used in reactive dyes: The substituents in formula (Ia) to formula (Ic) are the same as those defined in formula (I). "2N{|\ then a certain amount of hydrochloric acid is added, and then a sodium nitrite solution is added within 20 minutes to 30 minutes, controlled between diazotization (preferably between 0°C and 20°C), the end point of the reaction is determined by the ethanol solution of 4-dimethylaminobenzaldehyde (i.e. If there is no color change within 5 seconds, the end point has been reached); The molar ratio of each of the compounds of formula (Ia), formula (Ib) and/or formula (Ic) with respect to hydrochloric acid and sodium nitrite is 1: (1-3): (1-1,1), (2) coupling reaction: First Typically, 3,5-diaminobenzoic acid is dissolved in water, the pH of the solution is controlled to be between 8.0 and 12.0, and the temperature of the solution is controlled to be between 15°C and 25°C. Dissolved 3,5-diaminobenzoic acid solution (1) above. The formula (Ia) prepared in step 1 is added to the diazonium solution. The pH is controlled to be between 2.0 and 6.0 with liquid alkali or sodium bicarbonate, the temperature is controlled to be between 0°C and 20°C, and the first coupling reaction is carried out, the first reaction solution is tested with H acid test solution, dye is applied to the test piece. if it is uncontaminated, it means that the diazonium has completely reacted up to the end point, thus obtaining the 1st coupling product; secondly, (1). The diazonium solution of formula (Ib) or formula (Ic) prepared in step 1 is added to the coupling product, the pH is controlled to be between 5.0 and 8.0 with liquid alkali or sodium bicarbonate, the temperature is between 0°C and 20°C. is checked and the second coupling reaction is carried out, the second reaction solution is tested with H acid test solution, if the test piece is not contaminated with dye, it means that the diazonium has completely reacted to the last point, thus the 2nd coupling product is obtained; thirdly, (1). The diazonium solution of formula (Ib) or formula (Ic) prepared in step 2 is added to the coupling product, the pH is controlled to be between 5.0 and 8 with liquid alkali or sodium bicarbonate, the temperature is controlled to be between 0°C and 20°C, and the third coupling reaction is carried out, the third reaction solution is tested with H acid test solution, if the test piece is not contaminated with dye, it means that the diazonium has completely reacted to the end point, thus the reactive dye compound of formula (I) according to the present invention. Here, in each coupling reaction, the formula Moreover, if both D1 and D2 are groups of formula (a) or formula (b), the second coupling reaction and the third coupling reaction can be combined into a single coupling reaction, i.e. ( one). The diazonium solution of formula (Ib) or formula (Ic) prepared in step 1 is added to the coupling product, the pH is controlled to be between 5.0 and 8 with liquid alkali or sodium bicarbonate, the temperature is controlled to be between 0°C and 20°C. and the second coupling reaction is carried out, the second reaction solution is tested with H acid test solution, if the test piece is not contaminated with dye, it means that the diazonium has completely reacted to the end point, thus obtaining the reactive dye compound of formula (I); where the molar ratio of the compound of formula (Ib) or formula (Ic) with respect to 3,5-diaminobenzoic acid is (1,SJ-2,4): In the dark blue to black reactive dye composition according to the present invention, the dye compounds bonded in the ortho position of the phenolic hydroxyl are generally stable They are in a quinohydrazone state, that is, the dyes of the general formula (VI) contain essentially the quinohydrazone structure of the following formula (VIa) and/or formula (VIb) and/or formula (VIc) and/or formula (VId) and the general formula (II) ) and formula (IV) essentially contain the quinohydrazone structure of the following formula (IIa) and formula (IVa), respectively. Considering the writing habits of persons skilled in the art, the azo-form is also used as written form in the summary of the invention and in the examples, this The situation does not affect the essence of the present invention: 4 Ã:\IN_ N\ N :N4<:|: HO3 S 803 H R19(IVa) D5-N-N= \ D5-N=N Dö (VIa) D6 (VIb) D5-N= N D5-N-N: \ The definitions of the substituents of formula (IIa) and formula (IVa) above are the same as those of formula (II) and formula (IV), respectively, and the definitions of the substituents of formula (VIa) to formula (VId) are those of formula (VI). It is the same as . In addition, in the dark blue to black reactive dye composition according to the present invention, component A is at least one selected from the group consisting of compounds of formula (I) and their alkali metal salts, component B is at least one selected from the group consisting of compounds of formula (II) and their alkali metal salts. , component C is at least one selected from the group consisting of compounds of formula (111) to formula (IV) and their alkali metal salts, and component D is at least one selected from the group consisting of compounds of formula (V) to formula (VII) and their alkali metal salts; When the compound is an alkali metal salt, the carboxyl groups and sulfonic acid groups of formula (1) to formula (VII) exist in the form of the carboxylic acid or the alkali metal salt of the sulfonic acid. Preferably, the alkali metal salt is the sodium salt or potassium salt. The dye in the free acid form It is known to those skilled in the art that compounds and dye compounds in the form of alkali metal salts (such as sodium salt, potassium salt, etc.) have the same dyeing properties and that the structural formula of each monochromatic dye compound is generally expressed in the free acid form. However, in the actual synthesis process, They are usually prepared and isolated in alkali metal salt form (such as sodium or potassium salt) and are also used for dyeing in salt form, which is well known to those skilled in the art. The method of preparing the dark blue to black reactive dye composition according to the present invention involves mixing the dye components according to said ratio. Mixing can be accomplished by conventional mechanical means such as a grinder, kneader or homogenizer. In the mixing process, the individual dye compound may be present in the form of powder, granules, an aqueous solution or a synthetic solution. When the individual dye compound is mixed in the form of a synthetic solution, separation of the dark blue to black reactive dye composition according to the present invention from the synthetic solution can be accomplished by a generally known method, for example, by salting the dye and filtering it through a reaction medium with an electrolyte salt (such as sodium chloride or potassium chloride) or by evaporating the mixture. and spray dried. Therefore, paint components and their paint compositions generally contain the usual electrolyte salt(s) commonly seen in reactive paints (sodium chloride, sodium sulfate, etc.). When sold as a commodity or used directly, the dark blue to black reactive dye composition according to the present invention may be free of excipients and may also contain a cosolvent, a dispersant, an alkali-resistant excipient, a dustproofing agent, a surfactant, a buffer, and an accelerator, such as those common in commercial dyes. It can also be added with an auxiliary substance used as Therefore, the present invention also provides a dark blue to black reactive dye product comprising a dark blue to black reactive dye composition. Preferably, the dark blue to black reactive dye product comprises the dark blue to black reactive dye composition and an excipient. The weight of the auxiliary substance does not exceed 45%, preferably 40%, of the weight of the dark blue to black reactive dye composition. The excipient is preferably one or more compounds selected from the group consisting of: a naphthalene sulfonic acid/formaldehyde condensation product (NNO), a methylnaphthalenesulfonic acid/formaldehyde condensation product (dispersant MF), a diffusion agent CNF (benzylnaphthalenesulfonate/formaldehyde condensation product), Yuanming powder (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium hydrogencarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener and the like. All excipients are conventional products available on the market. The dark blue to black reactive dye product according to the present invention is suitable for dyeing and printing cellulose fibers, polyamide fibers and their fabrics, which may be nitrogen-containing and/or hydroxyl-containing fiber materials. Here, the cellulose fiber is preferably cotton fiber or regenerated fiber and may of course include other vegetable fibers such as hemp fiber or fabrics thereof; The polyamide fiber preferably includes animal fiber material such as leather, wool or silk, and synthetic fiber material such as nylon 6 and nylon 66. When the above-mentioned fiber material is dyed and printed using the dark blue to black reactive dye product according to the present invention, it can be carried out according to the known reactive dye dyeing and printing methods, such as the commonly used reactive dye dip dyeing method and scarf dyeing method, and the dip dyeing method is used to dye the fabric gradually. It is a method of dipping a fabric in a dyeing solution and usually needs to go through dyeing, fixing, washing, soaping, washing, dehydration, drying and similar processes. Scarf dyeing method is a method of first dipping the fabric in a dyeing solution, then passing the fabric through a roller, permeating the dyeing solution evenly into the interior of the fabric, and then treating the fabric by steaming, hot dissolving or other processes, and is usually scarfed with a dye solution, drying ( scarfing with fixing solution), steaming or curing, washing, soaping, washing, drying, etc. In general, due to different requirements for the dyed color of fabrics, the usage amount of dyes is different. When dyeing by immersion dyeing, the dyeing depth (owf) is usually between 0.1% and 10% (this is defined as the ratio of the weight of the dye to the dyeing solution by weight of the fabric, from 0.1% to 10% of the weight of the fabric), the initial dyeing temperature is 30° It is controlled to be between C to 60°C, dyeing time is 10 minutes to 30 minutes, soaping temperature is 85°C to 95°C, soaping time is 10 minutes, fixed pH is 9 to 11. When the scarf is dyed with the dyeing method, the dye shrinkage of the cellulose fiber is from 10 to 3 minutes. In scarf methods, the cold scarf dyeing method is commonly used, in which a dye and an alkaline substance are introduced into a scarf dyeing machine, wound on a roll, and the coated roll is rotated slowly at room temperature for 2 hours to 30 hours for setting and then rinsed thoroughly. The advantages of the present invention are that, when used for dyeing and printing nitrogen-containing and/or hydroxyl-containing fiber material, the dark blue to black reactive dye composition and product of the present invention have substantially good deposition, good compatibility, a high degree of fixation and color fastness, especially excellent washing fastness and the like. It is embodied in having qualities. Brief Description of the Drawings Figure 1 is the mass spectrum of the compound (I-1) obtained in example 1. Figure 2 is the mass spectrum of the chromophore (A) obtained in example 1. 10 Specific Embodiments The present invention will be explained in more detail in connection with the specific examples, but the scope of protection of the present invention is not limited to: The dye compounds used in the examples of this invention, 9 sodium in the actual synthesis process It is prepared and separated in its salt form and is also used in its sodium salt form for dyeing, but for ease of writing, all chemical formulas of the dye compounds in the examples are expressed in the free acid form and their important dyeing qualities are equivalent to the sodium salt form. (1) Diazotization: whisk for about 1 hour, add with hydrochloric acid, and add with. The diazotization reaction is carried out for 1 to 2 hours, controlling the pH between 0.5 and 2.0 and the temperature T between 0°C and 20°C, and the end point of the reaction is determined with an ethanol solution of 4-dimethylaminobenzaldehyde (i.e., color within 5 seconds). If there is no change, the end point is reached). After diazotization, excess sodium nitrite is eliminated with sulfamic acid to obtain a diazonium solution of 4-(acetylamino)-2-amino-benzenesulphonic acid and stored for use. is added, mixed for about 1 hour, 31% hydrochloric acid solution is added. The diazotization reaction is carried out for 1 to 2 hours, controlling the pH between 0.5 and 2.0 and the temperature T between 0°C and 20°C, and the end point of the reaction is determined with an ethanol solution of 4-dimethylaminobenzaldehyde (i.e., color within 5 seconds). If there is no change, the end point is reached). After diazotization, excess sodium nitrite is eliminated with sulfamic acid and the diazonium solution of the para-ester is obtained and stored for use. (2) Coupling reaction: It is controlled between 9.0 and the temperature of the solution between 20°C and 25°C. After whisking, (1). 0.1 mol of 4-(acetylamino)-2-amino-benzenesulfonic acid diazonium solution obtained in the step is added to the 3,5-dihydroxybenzoic acid solution. The pH is controlled to 5 to 5.5 with 30% liquid alkali, the temperature is controlled to 5 to 10°C, the reaction is carried out for 0.5 to 2 hours, and the free 3,5-dihydroxybenzoic is determined by HPLC. When the acid content is determined to be below 3%,10 the reaction reaches its final point and thus the chromophore of the following formula (A) is obtained, whose mass spectrum is shown in Figure 2. H3COCHN H2N (A) (1). The diazonium solution of the para-ester obtained in step is added to the chromophore of formula (A), the pH is controlled to be between 5 and 5.5 with 30% liquid alkali, and the temperature is controlled to be between 5°C and 10°C, the coupling reaction is 0 It is carried out for 5 to 10 hours. The reaction solution is tested with H acid test solution, if the test piece is not contaminated with dye, it means that the diazonium has completely reacted to the end point, thus an orange reactive dye compound (I-1) is obtained, its Amax value is 420 nm in water. And the mass spectrum of the compound (I-1) is shown in Figure 1. SO3H COOH N=N N=N@sozcHzcHzoso3H H3COCHN H2N NH2 Examples 2 to 66: Referring to the method of preparation of the azo dye described in Example 1, dye compounds with the structure shown in table 1 below, respectively, by stepwise diazotization using raw materials of intermediates well known in the art and obtained by coupling reactions. Example: Amax Reactive dye compounds (nm) 2 sogH COOH Hogs N 425 H0330H SO3H COOH HO3S 11 [ü] 425 H0330H N= N=NÜSOZCHZCHZOSOSH H3COCHN HZN NH2 12 [UI N=N N=NQSOZCH2CHZOSO3H 14 w 415 SOZCHZCHzososH (I 14) SO3H COOH [ü] 420 SO2CH2CHZOS O3H (I 15) sogH COOH H3CO 16 lü] 415 SO3H C 0 OH H3CO N=N N=N SOZCH2CH20803H H3COCHN HZN NH2 17 H 415 18 [|\|I 410 HOSSOHZCH2CO2S (I 18) 19 In] 410 HO3SOH2CH2COZS (I 19) 803H COOH H3CO N=N N=N SOZ CH2CH20803H H2NOCHN HZN NH2 OCH3 N 415 3 COOH H3CO 21 N 415 (1-21 ) 3 COOH H3CO H2NOCHN HZN NH2 CH3 22 ll 415 H2N NH2 23 N 410 chOCHN N=N N=NQSOzcHzcHzososH H2N NH2 N 415 (1-25) H2N NH2 N =n H H2N H2N NH2 ii 415 2 NH2 SO2CH2CH2OSO3H 31 w 410 SO2CH2CH2OSO3H (1_31) H3CH2C H2N NH2 32 'N 410 H2N NH2 H038H2C H2N NH2 34 [LI] 415 H2N NH2 3 5 IU] 4 10 HO3S N=N N=N SOZCHZCH20803H H2N HZN NH2 36 [UI 4 1 8 H2N N =N N=NQSOZCHZCH20803H H2N NH2 37 N 418 SOZCHZCHZOsogH (1-37) H2N N=N N=N H2N NH2 SOZCHZCHZOSO3H 3 8 H 418 I `SOZCHZCHZOSO3H (1-38) H2N NH2 SOZCHZCH20803H 39 435 HOg SOH2CH2COZS (1_39) HZNOCHN@N=N N =N .o H2N NH2 SOZCHZCH20803H 40 435 HO3SOHZCHZCOZS (1_40) H3COCHN@N=N Ni-i2 . E 'E `SOZCH2CH20803H CH3 COOH SO3H H3COCHN N=N N=N .o H2N NH2 SOZCHZCHZOSO3H 42 435 H0380H2CHZCOZS (1-42) 3 COOH SO3H H2NOCHN N=N N=N .o H2N NH2 SOZCHZCHZOsosH 43 435 HOg SOHzcHZCOZS (1_43) SO3H COOH SOsH HgCOCHN SOZCH20H20803H SO3H COOH SOsH SO3H COOH H3COCHN4ÖINHZN =NN N= N 46 435 . I SOZCHZCH20803H (1-46) SO2CH2CH2OSO3H H2NOCHNÖN=N N=N O H2N NH2 I I SOZCHZCH2OSOSH (1-47) H3COCHN@N=N N=NQSO2CH=CH2 H2N NH2 H2NOCHN N=N NINAQEIQCH: -CH2 50 H 418 SO3H COOH H300 H3COCHN N= N N=N 8020H=CH2 H2N NH2 51 N 418 HSCOCHN4®~N=N ?Q 2 SO2CH= CH2 52 'N' 415 H2NOCHN HZN SOZCH= CH2 53 TI' 425 H3COCHN N=N N=N SOZCH=CH2 H2N NH2 54 lu ] 422 H2NOCHN N=N N=N SOZCH=CH2 H2N NH2 55 [UI 422 803H COOH Hogs HscOCHNÖN=N N=N4©ýNHCOCHZCHZSOZCHZCHZCI H2N NH2 56 [LI] 428 NHCOCHZCHZSOZCHZCHZCI (1-56) HWOCHNÖN-N QNHCOCHZCHZSOZCHZCHzosoaH H2N NH2 57 [ LI] SO3H SOsH chOCHN N=N N=N H2N NH2 CONHCHZCHZSOZCHZCHzosogH 59 T" 420 CONHCHZCHZSOZCHZCHzosogH (1_59) 60 'H' 430 803" COOH HZNOCHNÖN=N N=NQCONHCHZCHZSOZCHZCHZOsoaH H2N NH2 N NH2 303" COOH N=N N=N4©ýSOZCH=CH2 H3COCHN H2N NH2 HO3SOH2CH2COZS (1-64) 803H COOH 803H H2N SOZCH20H20803H chOCHN NH2 02N N=N N=NQSOZCHZCH20803H It is mixed as H2N NH2 and with the resulting dye composition, cotton and especially nylon are dyed black by ordinary dip dyeing. and washing fastness of dyeing on wool (ISO 105 C10- accumulation and fixation degree is excellent. HZC=HCOZS@N=N:":N=N@SOZCH=CH2 HO3S SO3H ( ÖNN N=NQSOZCH2CHZOSOSH (1-1) 11-1) sodium sulfate powder is mixed mechanically and the resulting dye composition is applied to cotton by conventional dip dyeing. It is dyed black, and the degree of deposition and fixation of the dye, especially on nylon and wool (according to ISO 105 / T2391-2014), is excellent. and with the dye composition obtained, cotton is dyed dark black with the usual dip dyeing and the dye on nylon and wool in particular (ISO N=N N=NQSOZCH2CHZOSOSH HO38002H4OZS@N=N OC N49502C2H4OSO3H 21 parts of formula (I-1) dye, 76 parts of formula (II) -3) dye, 1 part of formula (IV-1) dye, 2 parts of formula (VI-26) dye, 10 parts of sodium sulfate powder and 10 parts of dispersant MF are mechanically mixed and with the resulting dye composition, cotton is dyed dark black and especially nylon and perfect. 1) dye, 68 parts formula (II) -3) dye, 7 parts of formula (IV-1) dye, 8 parts of formula (VI-26) dye, 10 parts of sodium sulfate powder and 10 parts of dispersant MF are mixed mechanically and with the resulting dye composition, cotton is dyed dark black and especially It is nylon and perfect. N=n a is dyed and especially nylon and The degree of deposition and fixation of the dye on wool (according to ISO GB / T2391-2014) is excellent. 803" COOH FORE" N=NQSOZCH2CHZOSOSH H20=Hcozs4®ýN=N MQSOZCH= -CH2 HO3S SO3H (11 SO3H (111_1) Examples 73 to Example 224: According to the method disclosed in one of Examples 67 to Example 72, listed in Table 2 The dyes in the proportions are mixed mechanically and the resulting dye mixture is dyed from cotton to dark blue to black by the conventional reactive dyeing method, and the degree of accumulation and fixation of the dye, especially on nylon and wool, is excellent. Example A Component Component C Ratio 73 (1-1) (II-3) _ 50:50 74 (1-1) (II-1) _ 45: 55 76 (1-4) (II-3) _ 35:65 77 (1-4) (II-1) _ 30:70 79 ( I-6) (II-3) _ 25:75 80 (I-6) (II-1) _ 15:85 82 (1-2) (II-3) _ 5:95 83 (1-2) ( II-1) _ 12:88 85 (1-5) (II-3) _ 24:76 86 (1-5) (II-1) _ 36:64 88 (1-7) (II-3) _ 38:62 89 (1-7) (II-1) _ 44:56 91 ( 20805 95 ( 45:55:25 (11-1)+(11- (111-1)+ (111-1)+ ( 111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111-1)+ (111- 1)+ : 95:10 :90:30 (111-2)+ _ _ (111-4)+ _ (111-2)+ :+ _ _ :75:15 :70:20 :+ _ _ 23: 77: 20 32:68: 10 (111-17)+ _ _ (111-20)+ _ (111-22)+ _ _ (11-10) (18+18):64:(5+5) ( 1-66) 21:79; (10+10) (1-29) 27:73: (8+8) (1-30) :65: (7+7) (1-3 1)+(I- (11-12) (1- 33) 45:55: (2+2+2) (1-34) 38:62: (5+5+5) (1-35) 34:66: (8+8+8) (15+15) : 70: (6+6+6) (1-3 8) ; (40+40)= (10+10+10) (1-39) ; (40+45)= (15+15+15) ( 1-40) :80: (5+5+5+5) (1-41) (1-42) (1-43) :65: (5+5+5+5+5) (144) (11) -11) 40:60: (5+5+5+5+5) (147) (11-12) 50:50: (4+4+4+4) (1-45) 45:55(5+ 5+5) (20+20): 60: (10+10+10) (1-50) (1-51) (1-52) (1-53) (1-56) (1-57) ( 1-58) (159) (11-11) :70:(7+7+7+7) (1-60) 38:62:(8+8+8+8) (1-61) 26:74 :(6+6+6+6) (1-64) (1-65) 50:50:(3+3+3+3) (1-66) 48 :52 : (4+4+4+4 ) (1-55) 45:55:(5+5+5) (111-40)+ (111-30)+ (111-20)+ (111-1)+ (111-2)+ (111- 4)Reactive black dye containing + 219 (1-54) 220 (1-53) is prepared: HO According to the method, the reactive black dye consisting of the following three components is prepared: ) and comparison example The dried reactive black dyes obtained in Example 1 and comparative Example 2 are respectively dissolved in water and added with sodium sulfate powder to prepare a dyeing solution with a final concentration of 50 g/L. Dyeing concentration (dye based on fabric weight) is set to 4%, bath ratio (weight of fabric in grams / volume of dyeing solution in millilitres) is set to 1:20, cotton is placed in the bath for adsorption at 60°C for 30 minutes, 45 minutes. Alkali (sodium carbonate 209 / L) is added for dye fixation, the dyed fabric is washed with water, soaped and dried for dyeing, thus dyed from dark blue to black and carried out according to the methods in ISO 105 X12. The results appear in table 2: Washing fastness Perspiration resistance Rubbing fastness Examples Dyeing strength Color Cotton Nylon Wool change Acid Alkaline Dry Wet dyeing dyeing dyeing compare compare Application Example 2: Representative examples 67 to 72 of the present invention and comparative examples 1 and 2 The accumulation nature of the reactive dyes obtained in is tested according to a method specified in the GB/T 21875-2016 standard and it is found that the deposition of the reactive dyes of examples 67 to 72 is clearly better than that of comparative examples 1 and 2 and that the amount of dye is It has been shown that it can be reduced by 5 to 15%, resulting in a significant economic impact. Application Example 3: The degree of fixation of the reactive dyes obtained in representative examples 67 to 72 of the present invention and comparative examples 1 to 2 is tested according to the method specified in the GB/T2391-2014 standard and the results are shown in Table 3: .. Example Example Example Example Example Example Comparison Comparative Examples .. " v' grade In summary, the dyes according to the present invention are significantly superior to the comparative examples and provide significant improvement in fastness, deposition and fixation for industry.TR TR
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| Publication Number | Publication Date |
|---|---|
| TR2023006438T2 true TR2023006438T2 (en) | 2023-08-21 |
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