US3519625A - Etherified methylolated melamines and process for finishing cellulosic textile material therewith - Google Patents
Etherified methylolated melamines and process for finishing cellulosic textile material therewith Download PDFInfo
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- US3519625A US3519625A US622400A US3519625DA US3519625A US 3519625 A US3519625 A US 3519625A US 622400 A US622400 A US 622400A US 3519625D A US3519625D A US 3519625DA US 3519625 A US3519625 A US 3519625A
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- Prior art keywords
- dyed
- direct
- fabric
- textile material
- cellulosic textile
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- 239000000463 material Substances 0.000 title description 15
- 239000004753 textile Substances 0.000 title description 14
- 238000000034 method Methods 0.000 title description 8
- 229920000877 Melamine resin Polymers 0.000 title description 4
- 150000007974 melamines Chemical class 0.000 title description 3
- 239000004744 fabric Substances 0.000 description 26
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- -1 METH MELAMINES Chemical class 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000982 direct dye Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920003180 amino resin Polymers 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 238000005562 fading Methods 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- YSLBFFIVJGJBSA-UHFFFAOYSA-N (4-ethylphenyl)methanol Chemical compound CCC1=CC=C(CO)C=C1 YSLBFFIVJGJBSA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- OYUZMQYZGSMPII-UHFFFAOYSA-L disodium 4-hydroxy-7-[(5-hydroxy-6-phenyldiazenyl-7-sulfonatonaphthalen-2-yl)amino]-3-phenyldiazenylnaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(Nc3ccc4c(O)c(N=Nc5ccccc5)c(cc4c3)S([O-])(=O)=O)ccc12)S([O-])(=O)=O OYUZMQYZGSMPII-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical group COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UFUQRRYHIHJMPB-DUCFOALUSA-L Sirius red 4B Chemical compound [Na+].[Na+].OS(=O)(=O)c1cc2cc(NC(=O)c3ccccc3)ccc2c([O-])c1\N=N\c1ccc(cc1)\N=N\c1ccc(cc1)S([O-])(=O)=O UFUQRRYHIHJMPB-DUCFOALUSA-L 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical class OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- DSARWKALPGYFTA-UHFFFAOYSA-L disodium 4-hydroxy-7-[(5-hydroxy-6-phenyldiazenyl-7-sulfonatonaphthalen-2-yl)carbamoylamino]-3-phenyldiazenylnaphthalene-2-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(NC(=O)NC=3C=C4C=C(C(N=NC=5C=CC=CC=5)=C(O)C4=CC=3)S([O-])(=O)=O)=CC=C2C(O)=C1N=NC1=CC=CC=C1 DSARWKALPGYFTA-UHFFFAOYSA-L 0.000 description 1
- YCMOBGSVZYLYBZ-UHFFFAOYSA-L disodium 5-[[4-[4-[(2-amino-8-hydroxy-6-sulfonatonaphthalen-1-yl)diazenyl]phenyl]phenyl]diazenyl]-2-hydroxybenzoate Chemical compound NC1=CC=C2C=C(C=C(O)C2=C1N=NC1=CC=C(C=C1)C1=CC=C(C=C1)N=NC1=CC=C(O)C(=C1)C(=O)O[Na])S(=O)(=O)O[Na] YCMOBGSVZYLYBZ-UHFFFAOYSA-L 0.000 description 1
- DDLNJHAAABRHFY-UHFFFAOYSA-L disodium 8-amino-7-[[4-[4-[(4-oxidophenyl)diazenyl]phenyl]phenyl]diazenyl]-2-phenyldiazenyl-3,6-disulfonaphthalen-1-olate Chemical compound [Na+].[Na+].NC1=C(C(=CC2=CC(=C(C(=C12)O)N=NC1=CC=CC=C1)S(=O)(=O)[O-])S(=O)(=O)[O-])N=NC1=CC=C(C=C1)C1=CC=C(C=C1)N=NC1=CC=C(C=C1)O DDLNJHAAABRHFY-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical class O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- FKVXIGHJGBQFIH-UHFFFAOYSA-K trisodium 5-amino-3-[[4-[4-[(7-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3[O-])N)S(=O)(=O)O)N=NC5=C(C6=C(C=C(C=C6C=C5S(=O)(=O)O)S(=O)(=O)[O-])N)[O-].[Na+].[Na+].[Na+] FKVXIGHJGBQFIH-UHFFFAOYSA-K 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
Definitions
- etherified methylolated melamines of For- This invention relates to new and etherified methylmula I impart crease-resistant properties to cellulosic texoleated melamines and their use on cellulosic textile matile materials without adversely affecting the lightfastness terials dyed with direct dyes.
- the new etherified melaof such material dyed with direct dyes This is a surprismines impart crease-resistance to such materials and the ing discovery since cellulosics dyed with direct dyes are light-fastness of the direct dyes is improved. normally adversely afiected as to lightfastness when aftertreated with aminoplast textile finishes.
- the textile finishing aminoplast resins used in this invention are applied to direct-dyed cellulosic textile ma-
- This invention relates to new compounds and to textile t i l b tandard procedures, as by dipping, padding, finishes for dyed cellulosic textile materials. More parspraying, etc., and the finishes are converted to an inticulafly, it relates to etherified m r hy e soluble state by heating the treated fabrics in the presence precondensates and their use on cellulosic textile mateof a atalyst, The dyed materials thus treated exhibit rials dyed with direct dyes. Still more particularly, it crease-resistant. and wrinkle-recovery properties, and a relates to the use of new etherified methylolated melalightfastness equal to, or even better than the untreated, mines of the Formula I: 3 dyed material.
- the compounds of Formula I can be made by reacting I an N-halomethylmelamine of Formula II with an alkali metal salt of Formula III as above: N
- N CH2O alkyl wherein X is chlorine or bromine, M is an alkali metal, (alkyl-OOHzhN- and alkyl and R are as defined above for Formula I. N CHz-OCHz-
- X chlorine or bromine
- M is an alkali metal
- alkyl-OOHzhN- and alkyl and R are as defined above for Formula I.
- N CHz-OCHz- The compounds of Formula II and a process for their manufacture are disclosed and claimed in US. Pat. No.
- alkyl is a lower-alkyl group (1-4 C atoms) and Representative N-halomethylmelamines of Formula II R is hydrogen, alkyl of up to 18 C atoms, phenyl or which can be used in this invention include N-chlorophenyl(lower-a1kyl), any of the phenyl or said R groups, methyl N,N',N,N",N"-pentakis(methoxymethyl)2,4,6-
- R is aryl, having up to two inert radicals, triamino-s-triazine, N-bromomethyl-N,N,N,N",N"-pensuch as lower-alkyl and lower-alkoxy groups.
- takis(methoxymethyl)-2,4,6-triamino-s-triazine, N-bromo- The use of aminoplast resins to impart crease-resistance methyl N,N,N,N",N" pentakis (ethoxymethyl)-2,4,6- to cellulosics is well-known.
- aminoplast pounds of Formula III is carried out with or without a crease-preventing finishes can cause accelerated fading of solvent, although it is preferable to use a solvent, parmany direct dyes, i.e., the lightfastness of cellulosic texticularly the alcohol from which the said alkali metal salt tile material dyed with direct dyes is often reduced when is prepared.
- the reaction is conveniently carried out at the dyed material is after-treated with an aminoplast resin room temperature, although any temperature between or reactant, such as a urea-formaldehyde or a melaminethe freezing and boiling points of the reaction mixture formaldehyde condensate.
- Commercial resins which have may be used.
- Equimolar amounts of reactants can be adbeen shown to cause fading of certain direct dyes include vantageously used, although an excess of either can be hexa(methoxymethyl)melamine, polymethylolurea with present without adverse effect.
- the cellulosic textile materials include fibers, threads, ated hexamethylolmelamine and urea-formaldehyde reacyarns, knitted and woven cloth as well as non-woven tion products, and methylated trimethylolmelamine. fabrics and felted materials. These cellulosic materials In view of the widespread use of both direct dyes and will normally contain at least 50% cellulosic fibers, such 3 as cotton, viscose, cuprammonium rayons, linen, hemp, jute and ramie, either alone or mixed with themselves or other fibers.
- the cellulosic textile materials will be dyed with the class of azo dyes known as direct dyes and so classified in the Color Index, second edition.
- Such dyes are characterized as anionic dyes having affinity for cellulosio fibers when applied from an aqueous dyebath containing an electrolyte. They are mainly azo dyes containing sulfonic acid groups as the sodium salts.
- Representative direct dyes are Direct Yellow 6 (0.1. 4001), Direct Yellow 11 (CI. 40000), Direct Orange 26 (Cl. 29150), Direct Red 1 (CI. 22310), Direct Red 31 (C.I. 29100), Direct Blue 2 (Cl. 22590), and Direct Green 1 (0.1. 30280).
- the amount of finish on the textile material can be varied, usually between 0.5% and 40% based on the Weight of the textile material, with amounts between 2.5% and 15% preferably being used for practical crease-resistant and Wrinkle-recovery properties.
- the treated fabrics are dried and then heated, preferably in the presence of a catalyst, to efifect insolubility of the precondensate on the fabric (cross-linking, etc). Curing temperatures between 275 and 400 F. for periods of about 20 minutes to 30 seconds are normally used.
- Suitable catalysts includes those normally used for melamine-formaldehyde condensates and their etherates. These include the metal salts such as magnesium chloride, zinc nitrate and zinc chloride, ammonium salts such as ammonium sulfate, ammonium chloride, and organic amine hydrochlorides. In the case of magnesium chloride, the amount is between about 4.5% and 24%, preferably between 9% and 15%, of the anhydrous salt based on the weight of the precondensate.
- the treated dyed fabric obtained by this convention will be found to have good wrinkle-recovery and creaseresistance normally required for commercial cellulosics. In addition, advantageously, they will be found to possess lightfastness not previously attained with fiJII'liIlOPlELSt resin-treated direct-dyed cellulosics.
- the unreacted benzyl alcohol is removed by vacuum distillation.
- the product a viscous liquid, is N-(benzyloxymethyl-N,- N,N,N,N"pentakis (methoxymethyl)-2,4,6-triaminos-triazine.
- Example 2 N CHzO CzHs b-N N CHzO-CHz-CuHa- 14(1
- the procedure of Example 1 is followed, substituting an equivalent amount of p-methoxybenzyl alcohol for the benzyl alcohol.
- the product is N-(p-methoxybenzyloxymethyl) N,N,N',N",N-pentakis(methoxymethyl)- 2,4,6-triamino-s-triazine.
- Pad baths are prepared containing 6.25 of precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.
- Pad Bath A N (benzyloxymethyl) N,N',N,N",N", pentakis- (ethoxymethyl)-2,4,6-tria-mino-s-triazine, the product of Example 1, in 85% aqueous dimethylformamide.
- Pad bath B N,N,N,N,N,N" hexakis(methoxymethyl) 2,4,6- triamino-s-triazine in water, for purposes of comparison.
- the pad baths are applied to x 80 cotton percale at 5% O.W.F. of precondensate solids by standard padding procedure using 80% Wet pickup.
- the treated fabrics are dried for 2 minutes at 225 F. and the finish is cured by heating the fabric at 350 F. for 1.5 minutes.
- the wrinkle recovery of the treated fabrics and a sample of untreated fabric is measured on a wrinkle recovery tester following tentative test method 66-1959T, described on page B-l43 of the 1964 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists.
- the strength loss due to retained chlorine is measured by standard test method 924962, described on page B-102 of the above reference, before and after five acid rinses.
- the acid rinses are carried out by immersing the fabric in an aqueous solution of zinc fluorosilicate followed by drying.
- finish A is superior to the other finish in resistance to damage caused by retained chlorine after five acid rinses.
- Pad baths are prepared containing 6.25% precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.
- Pad bath A N (benzyloxymethyl) N,N,N,N",N pentakis (methoxymethyl) 2,4,6 triamino-s-triazine product of Example 1) in acetone.
- Pad bath B N,N,N',N,N",N" hexakis(methoxymethyl) 2,4,6- triamino-s-triazine in water.
- the pad baths are applied to a sample of 80 x 80 cotton percale dyed with Direct Red 81 (CI. 28160) at 5% O.W.F. of precondensate solids by standard padding procedure using 80% wet pickup.
- the treated fabrics are dried for 2 minutes at 225 F., and the finishes are cured by heating the fabrics at 350 F. for 1.5 minutes.
- a sample of the dyed, but untreated, fabric is rinsed in water and dried. A portion of each of the fabrics of each color is washed in a home-style washing machine at 110 115 F. with water containing 0.25% of a commercial anionic surface active agent and 0.25% of sodium carbonate. The washed fabrics are dried.
- Spectrophotometric curves of the unexposed portion of dyed fabric and the exposed portion of dyed fabric are recorded for 21 wavelengths over the complete visual range.
- the spectrophotometric data are converted to colormetric data by means of a digital computer. Numerical expressions of color in terms of 3-dimensional color coordinates are thus obtained.
- the two sets of colorimetric data i.e., one set for unexposed fabric and one set for the exposed fabric, are then converted into a single color difference (in NBS units) by the system of Wyszecki, J. Opt. Soc. Am. 53, 1318 (1963).
- the evaluation of the colorimetric data can be done by computer.
- the single number color difference thus obtained can be considered in this instance to be strength ratio figures between exposed and unexposed fabric, negative numbers indicating loss in strength, i.e. fading.
- finish A is superior to finish B in resistance to light-fading and is generally superior to the untreated dyed fabric.
- alkyl is an alkyl group of 1-4 C atoms and R is hydrogen, alkyl of up to 18 carbons or lower-alkoxy.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
United States Patent "'ce 3,519,625
Patented July 7, 1970 aminoplast resins on cellulosics, it is extremely undesir- 3,519,625 able to have the use of the resin for its purpose, restrict ETHERIF D METH MELAMINES AND the functioning of the dye for its purpose. It is therefore IFA TIL ggg cggTlg an object of the present invention to provide a means of treating direct-dyed cellulosics with aminoplast resins Michael Thomas Beachem Somerset and Frederic Hough- 5 ton Megson Martinsvflle NJ assignors to American whereby crease resistance is imparted to the cellulosic with no substantial reduction in lightfastness. It is a fur- 332%}: Company Stamford Conn" a corporatmn ther object to provide cellulosics which have been direct No Drawing. Filed Mar. 13, 1967, Ser. No. 622,400 dyed and have improved lightfastness, while also exhibit- Int. Cl. C07d 55/22 10 ing good crease-resistance by virtue of treatment with a 5 Claims particular aminoplast resin textile improving agent. Other objects will be apparent from the ensuing description of this invention.
It has now been discovered in accordance with this in- ABSTRACT OF THE DISCLOSURE 15 vention that etherified methylolated melamines of For- This invention relates to new and etherified methylmula I impart crease-resistant properties to cellulosic texoleated melamines and their use on cellulosic textile matile materials without adversely affecting the lightfastness terials dyed with direct dyes. The new etherified melaof such material dyed with direct dyes. This is a surprismines impart crease-resistance to such materials and the ing discovery since cellulosics dyed with direct dyes are light-fastness of the direct dyes is improved. normally adversely afiected as to lightfastness when aftertreated with aminoplast textile finishes.
The textile finishing aminoplast resins used in this invention are applied to direct-dyed cellulosic textile ma- This invention relates to new compounds and to textile t i l b tandard procedures, as by dipping, padding, finishes for dyed cellulosic textile materials. More parspraying, etc., and the finishes are converted to an inticulafly, it relates to etherified m r hy e soluble state by heating the treated fabrics in the presence precondensates and their use on cellulosic textile mateof a atalyst, The dyed materials thus treated exhibit rials dyed with direct dyes. Still more particularly, it crease-resistant. and wrinkle-recovery properties, and a relates to the use of new etherified methylolated melalightfastness equal to, or even better than the untreated, mines of the Formula I: 3 dyed material.
compounds of Ifil N /CH2O-a1ky1+ M00112- Formulal MX (a1kyl-OOH2)zN-O b-N\ III N crux N(CH Q a1k 1) The compounds of Formula I can be made by reacting I an N-halomethylmelamine of Formula II with an alkali metal salt of Formula III as above: N
g N CH2O alkyl wherein X is chlorine or bromine, M is an alkali metal, (alkyl-OOHzhN- and alkyl and R are as defined above for Formula I. N CHz-OCHz- The compounds of Formula II and a process for their manufacture are disclosed and claimed in US. Pat. No.
' (1) 3,317,529, issued May 2, 1967 to Beachem et al. wherein alkyl is a lower-alkyl group (1-4 C atoms) and Representative N-halomethylmelamines of Formula II R is hydrogen, alkyl of up to 18 C atoms, phenyl or which can be used in this invention include N-chlorophenyl(lower-a1kyl), any of the phenyl or said R groups, methyl N,N',N,N",N"-pentakis(methoxymethyl)2,4,6-
especially when R is aryl, having up to two inert radicals, triamino-s-triazine, N-bromomethyl-N,N,N,N",N"-pensuch as lower-alkyl and lower-alkoxy groups. takis(methoxymethyl)-2,4,6-triamino-s-triazine, N-bromo- The use of aminoplast resins to impart crease-resistance methyl N,N,N,N",N" pentakis (ethoxymethyl)-2,4,6- to cellulosics is well-known. These resins perform their triamino-s-triazine, N-chloromethyl-N,N',N',N",N"-penfunction economically and efiiciently without adversely takis(butoxymethyl)-2,4,6-triamino-s-triazine, etc. affecting many of the other desirable properties of cellu- Representative compounds of Formula III include the losics, such as, for example, fabric hand, soil resistance sodium salts of benzyl alcohol, p-methylbenzyl alcohol, or fabric durability. However, aminoplast resins do in p-ethylbenzyl alcohol, etc. some cases have an adverse effect on color stability of The reaction of compounds of Formula II with comdyed cellulosics. Thus, it is well-known that aminoplast pounds of Formula III is carried out with or without a crease-preventing finishes can cause accelerated fading of solvent, although it is preferable to use a solvent, parmany direct dyes, i.e., the lightfastness of cellulosic texticularly the alcohol from which the said alkali metal salt tile material dyed with direct dyes is often reduced when is prepared. The reaction is conveniently carried out at the dyed material is after-treated with an aminoplast resin room temperature, although any temperature between or reactant, such as a urea-formaldehyde or a melaminethe freezing and boiling points of the reaction mixture formaldehyde condensate. Commercial resins which have may be used. Equimolar amounts of reactants can be adbeen shown to cause fading of certain direct dyes include vantageously used, although an excess of either can be hexa(methoxymethyl)melamine, polymethylolurea with present without adverse effect.
slight degree of methylation, blends of partially methyl- The cellulosic textile materials include fibers, threads, ated hexamethylolmelamine and urea-formaldehyde reacyarns, knitted and woven cloth as well as non-woven tion products, and methylated trimethylolmelamine. fabrics and felted materials. These cellulosic materials In view of the widespread use of both direct dyes and will normally contain at least 50% cellulosic fibers, such 3 as cotton, viscose, cuprammonium rayons, linen, hemp, jute and ramie, either alone or mixed with themselves or other fibers.
The cellulosic textile materials will be dyed with the class of azo dyes known as direct dyes and so classified in the Color Index, second edition. Such dyes are characterized as anionic dyes having affinity for cellulosio fibers when applied from an aqueous dyebath containing an electrolyte. They are mainly azo dyes containing sulfonic acid groups as the sodium salts. Representative direct dyes are Direct Yellow 6 (0.1. 4001), Direct Yellow 11 (CI. 40000), Direct Orange 26 (Cl. 29150), Direct Red 1 (CI. 22310), Direct Red 31 (C.I. 29100), Direct Blue 2 (Cl. 22590), and Direct Green 1 (0.1. 30280).
The dyed materialsrare treated with the textile finishes of this invention using aqueous or organic solvent solutions or dispersions which can be applied by spraying, dipping or padding according to well-known procedures. Between 0.5% and 40% solutions or dispersions are normally used. The amount of finish on the textile material can be varied, usually between 0.5% and 40% based on the Weight of the textile material, with amounts between 2.5% and 15% preferably being used for practical crease-resistant and Wrinkle-recovery properties. The treated fabrics are dried and then heated, preferably in the presence of a catalyst, to efifect insolubility of the precondensate on the fabric (cross-linking, etc). Curing temperatures between 275 and 400 F. for periods of about 20 minutes to 30 seconds are normally used.
Suitable catalysts includes those normally used for melamine-formaldehyde condensates and their etherates. These include the metal salts such as magnesium chloride, zinc nitrate and zinc chloride, ammonium salts such as ammonium sulfate, ammonium chloride, and organic amine hydrochlorides. In the case of magnesium chloride, the amount is between about 4.5% and 24%, preferably between 9% and 15%, of the anhydrous salt based on the weight of the precondensate.
The treated dyed fabric obtained by this convention will be found to have good wrinkle-recovery and creaseresistance normally required for commercial cellulosics. In addition, advantageously, they will be found to possess lightfastness not previously attained with fiJII'liIlOPlELSt resin-treated direct-dyed cellulosics.
The following examples are presented to further illustrate this invention.
EXAMPLE 1 N C H2 OHzCaHs A solution of 39.8 parts (0.01 mole) of N-chloromethyl N,N',N',N",N" pentakis(methoxymethyl-2,4,6= triamino-s-triazine in 54.1 parts (0.50) mole of benzyl alcohol is added slowly to the reaction mixture of 54.1 parts (0.50 mole) of benzyl alcohol and 2.39 parts (0.105 mole) of sodium at 2530 C. After a reaction period of about 24 hours, 100 parts of water is added. The organic layer is washed with 10% aqueous sodium hydroxide, sodium chloride solution and a 50:50 (by volume) mixture of methanol and water. The unreacted benzyl alcohol is removed by vacuum distillation. The product, a viscous liquid, is N-(benzyloxymethyl-N,- N,N,N,N"pentakis (methoxymethyl)-2,4,6-triaminos-triazine.
N CHzO CzHs b-N N CHzO-CHz-CuHa- 14(1 The procedure of Example 1 is followed, substituting an equivalent amount of p-methoxybenzyl alcohol for the benzyl alcohol. The product is N-(p-methoxybenzyloxymethyl) N,N,N',N",N-pentakis(methoxymethyl)- 2,4,6-triamino-s-triazine.
EXAMPLE 4 N(CH2O CH3):
CHQO CH (C1130 CHzhN- -N CHzO-CH2*CsHr-C2H5(D) The procedure of Example 1 is followed, substituting an equivalent amount of p-ethylbenzyl alcohol for the benzyl alcohol. The product is N-(p-ethylbenzyloxymethyl)-N,N',N,N",N-2,4,6-triamino-s-triazine.
EXAMPLE 5 Pad baths are prepared containing 6.25 of precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.
Pad Bath A N (benzyloxymethyl) N,N',N,N",N", pentakis- (ethoxymethyl)-2,4,6-tria-mino-s-triazine, the product of Example 1, in 85% aqueous dimethylformamide.
Pad bath B N,N,N,N,N,N" hexakis(methoxymethyl) 2,4,6- triamino-s-triazine in water, for purposes of comparison.
The pad baths are applied to x 80 cotton percale at 5% O.W.F. of precondensate solids by standard padding procedure using 80% Wet pickup. The treated fabrics are dried for 2 minutes at 225 F. and the finish is cured by heating the fabric at 350 F. for 1.5 minutes.
The wrinkle recovery of the treated fabrics and a sample of untreated fabric is measured on a wrinkle recovery tester following tentative test method 66-1959T, described on page B-l43 of the 1964 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists.
The strength loss due to retained chlorine is measured by standard test method 924962, described on page B-102 of the above reference, before and after five acid rinses.
The acid rinses (acid sours) are carried out by immersing the fabric in an aqueous solution of zinc fluorosilicate followed by drying. v
The measurements of finishes A and B corresponding to pad baths A and B, respectively, show the finishes to be about equivalent in degree of wrinkle recovery, but
CH2OCH3 that finish A is superior to the other finish in resistance to damage caused by retained chlorine after five acid rinses.
EXAMPLE 6 Pad baths are prepared containing 6.25% precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.
Pad bath A N (benzyloxymethyl) N,N,N,N",N pentakis (methoxymethyl) 2,4,6 triamino-s-triazine product of Example 1) in acetone.
Pad bath B N,N,N',N,N",N" hexakis(methoxymethyl) 2,4,6- triamino-s-triazine in water.
The pad baths are applied to a sample of 80 x 80 cotton percale dyed with Direct Red 81 (CI. 28160) at 5% O.W.F. of precondensate solids by standard padding procedure using 80% wet pickup. The treated fabrics are dried for 2 minutes at 225 F., and the finishes are cured by heating the fabrics at 350 F. for 1.5 minutes. Also a sample of the dyed, but untreated, fabric is rinsed in water and dried. A portion of each of the fabrics of each color is washed in a home-style washing machine at 110 115 F. with water containing 0.25% of a commercial anionic surface active agent and 0.25% of sodium carbonate. The washed fabrics are dried.
Samples of the treated fabrics, both washed and unwashed, are exposed in a Fade-Ometer for 60 hours, The degree of fading of the exposed samples of fabric is measured as follows:
Spectrophotometric curves of the unexposed portion of dyed fabric and the exposed portion of dyed fabric are recorded for 21 wavelengths over the complete visual range. The spectrophotometric data are converted to colormetric data by means of a digital computer. Numerical expressions of color in terms of 3-dimensional color coordinates are thus obtained. The two sets of colorimetric data, i.e., one set for unexposed fabric and one set for the exposed fabric, are then converted into a single color difference (in NBS units) by the system of Wyszecki, J. Opt. Soc. Am. 53, 1318 (1963). The evaluation of the colorimetric data can be done by computer.
The single number color difference thus obtained can be considered in this instance to be strength ratio figures between exposed and unexposed fabric, negative numbers indicating loss in strength, i.e. fading. The larger the color difference number, the greater the difference in the visual appearance between the two samples.
It is generally accepted that a color difference of 0.2 NBS unit is the minimum detectable amount which an experienced person can detect between two samples. The color difference for an acceptable commercial match is probably between 1.0 and 2.0 NBS units as discussed in the monograph by Judd, Color in Business, Science and Industry, Wiley, New York, 1952.
The results of the fading measurements are shown in Table I, finishes A and B corresponding to pad baths A and B, respectively.
TABLE I.-FADING IN NBS UNITS Initial Washed FinishA 7.0 11.1 Finish B -12. 6 16. 7 Untreated 10. 3 11. 3
TABLE I.-FADING IN NBS UNITS Initial Washed Finish A -7.0 11. 1 Finish B l2.6 -16.7 Untreated 10. 3 11. 3
It can be seen that finish A is superior to finish B in resistance to light-fading and is generally superior to the untreated dyed fabric.
We claim:
1. A compound of the formula:
wherein alkyl is an alkyl group of 1-4 C atoms and R is hydrogen, alkyl of up to 18 carbons or lower-alkoxy.
2. The compound according to claim 1 which has the formula:
3. The compound according to claim 1 which has the formula:
4. The compound according to claim 1 which has the ll (021- H2) 2NC 5. The compound according to claim 1 which has the formula:
Campbell et al.: J. Org. Chem., vol. 26, pp. 2786-9 1961 JOHN D. RANDOLPH, Primary Examiner I. M. FORD, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62240067A | 1967-03-13 | 1967-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3519625A true US3519625A (en) | 1970-07-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US622400A Expired - Lifetime US3519625A (en) | 1967-03-13 | 1967-03-13 | Etherified methylolated melamines and process for finishing cellulosic textile material therewith |
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| US (1) | US3519625A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3617181A (en) * | 1970-04-06 | 1971-11-02 | American Cyanamid Co | Process for finishing cellulosic textile materials with etherified melamines |
| US3878163A (en) * | 1971-07-01 | 1975-04-15 | Martin Dexter | 3,5-dialkyl-4-hydroxyphenyl alkanoic acid esters of 2,4,6-tris(alkanolamino) derivatives of triazine as antioxidants |
| US4006274A (en) * | 1975-09-19 | 1977-02-01 | The United States Of America As Represented By The Secretary Of Agriculture | 2,4,6-Tris(carbamoylmethylamino)-1,3,5,-s-triazine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2709693A (en) * | 1950-12-04 | 1955-05-31 | Ciba Ltd | Etherified condensation products of formaldehyde with amino-1:3:5-triazines containing at least two aminogroups |
| US2861054A (en) * | 1953-06-03 | 1958-11-18 | Montclair Res Corp | Water repellents techniques |
| US3422020A (en) * | 1965-02-11 | 1969-01-14 | Henkel & Cie Gmbh | Low-sudsing detergent compositions |
-
1967
- 1967-03-13 US US622400A patent/US3519625A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2709693A (en) * | 1950-12-04 | 1955-05-31 | Ciba Ltd | Etherified condensation products of formaldehyde with amino-1:3:5-triazines containing at least two aminogroups |
| US2861054A (en) * | 1953-06-03 | 1958-11-18 | Montclair Res Corp | Water repellents techniques |
| US3422020A (en) * | 1965-02-11 | 1969-01-14 | Henkel & Cie Gmbh | Low-sudsing detergent compositions |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3617181A (en) * | 1970-04-06 | 1971-11-02 | American Cyanamid Co | Process for finishing cellulosic textile materials with etherified melamines |
| US3878163A (en) * | 1971-07-01 | 1975-04-15 | Martin Dexter | 3,5-dialkyl-4-hydroxyphenyl alkanoic acid esters of 2,4,6-tris(alkanolamino) derivatives of triazine as antioxidants |
| US4006274A (en) * | 1975-09-19 | 1977-02-01 | The United States Of America As Represented By The Secretary Of Agriculture | 2,4,6-Tris(carbamoylmethylamino)-1,3,5,-s-triazine |
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