CA2073580A1 - Process for printing and photochemically stabilising polyester fibre materials - Google Patents
Process for printing and photochemically stabilising polyester fibre materialsInfo
- Publication number
- CA2073580A1 CA2073580A1 CA002073580A CA2073580A CA2073580A1 CA 2073580 A1 CA2073580 A1 CA 2073580A1 CA 002073580 A CA002073580 A CA 002073580A CA 2073580 A CA2073580 A CA 2073580A CA 2073580 A1 CA2073580 A1 CA 2073580A1
- Authority
- CA
- Canada
- Prior art keywords
- absorber
- formula
- c5alkyl
- hydrogen
- c5alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65112—Compounds containing aldehyde or ketone groups
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
- Treatment Of Fiber Materials (AREA)
- Polyesters Or Polycarbonates (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
Process for printing and photochemically stabilising polyester fibre materials Abstract of the Disclosure A process for printing and photochemically stabilising polyester fibre materials with disperse dyes and subsequently subjecting the materials to a heat treatment, which process comprises printing said materials with an aqueous print paste which, in addition to the disperse dye, contains a UV absorber.
The process makes it possible to obtain strong, washfast and rubfast prints with a good white ground. The prints are distinguished by superior lightfastness and the fibre material is photochemically stable.
The process makes it possible to obtain strong, washfast and rubfast prints with a good white ground. The prints are distinguished by superior lightfastness and the fibre material is photochemically stable.
Description
2~7~8~
l-t8712/A
Process for printin~ and photochemically stabilisin~ polyester fibre materials The present invention relates to a process for printing and photochemically stabilising polyester fibre materials with disperse dyes.
Processes for prinhng polyester fibre materials with disperse dyes are known, inter alia from DE-A-3 918 603. The printing inks applied in the process of this patent speci~lcation and the fibre materials are, however, materially damaged by the action of light and simultaneous exposure to heat. In the automotive sector or in the swimwear sector or, for example, in the field of furnishing fabrics, where exacting demands are made of the lighfastness of printing inks and of the photochemical stability of the fibres, it is not possible to use the printed fabrics obtained by this process.
It is therefore the object of this invention to provide a process for printing polyester fabrics, which makes it possible to stabilise polyester fabrics photochemically and to enhance the lightfastness of the printing inks appIied to said ~abrics.
It has now been found that, by using a print paste which contains a UV absorber, on the one hand the fabric is stabilised photochemically and enhanced lightfastness is imparted to the printing inks andj surprisingly, on the other, that markedly better colour yields are also obtained.
.
The invention accordingly provides a process for printing and photochemically stabilising polyester fibre materials with disperse dyes and subsequendy subjecting the materials to a heat treatment, which process comprises printing said materials with an aqueous print paste which, in addition to the disperse dye, contains a UV absorber.
UV Absorbers suitable for the inventive process are those which are resistant tosublimation at temperatures up to 165C.
The UV absorbers present in the print paste are suitably compounds of the class of the hydroxyphenyl-s-triazines which have the formula 2~73~
2 1~89-8~g7 ~OH
~1) .
N~N
11 .
P(1 N R2 whereln R is Cl-Csalkyl, Cl-CsaLkoxy, halogen~ hydroxy, l and R~ are each independently of the other Cl-Cl8aL~cyl, Cl-CI8alkyl which issubstituted ~y hydroxy, Cl-Csalkoxy, Cl-C~jalkylthio7 amino or Cl-Cs-mono- or Cl-C5-dialkylarnino, phenyl or phenyl which is substituted by chloro, hydroxy, Cl-CsaL~yl and/or Cl-CI2aL~oxy, or a rad;cal of fonnula ( 0 C H 2 - C H 2 ) p O -~R
n isO,lor2, p is 1 to 5 and R3 is hydrogen or Cl-Csalkyl.
::
R, R~ 2 and R3 as alkyl may be straight-chain or branched and are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-bu~yl, tert-butyl, pentyl, isopen~yl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isonony1, n-dodecyl, heptadecyl or oetadecyl.
Cl-C:sAlkoxy or Cl-Csalkylthio may be me~oxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, rnethylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio or tert-pentylthio.
Examples for mono-Cl-CsaLkylamino are monomethyl-, monoethyl-, monopropyl-, monoisopropyl-, monobutyl- or monopentylamino. Examples for di-CI-C5alkylamino are dimethyl-, methylethyl- or diethylamino.
21~8g-8497 3 2~73~8~
H~108en w~ll bo ~on t¢ moaA fluoro, bromo or, pre~rably, chloro. ~ ., Importarlt ~-lsiazine~ are those of fonnula .
a OH
N N
` ~ J~NJ~RB
.. . . .
wherein R ig hydrogcn or has ~he meaning glvel~ ~n fonnula(l), ~nd R~ and Rs ~ each indopendently of lho other un~ubst~tuted phenyl or phenyl subs~nlted by Cl-Csalkyt ~nd/or Cl-Csallcoxy, p: is l to S, and R6 ~8 hyd~ogen or C~ 5alkyl.
: . Other p~ifcmid ~iszlne~ ~ Ihoso of ~osmula (3) ~OH
N
whercin ~7 i~ Cl-Cs~kyl or C1 -C5alkoxy, R~ ~nd R~ are eacll independently of tho other unsubstitu~ed phenyl or phcnyl bslltulcdby Cl-CsalkylandlorCI-C5alkoxy or a radiral o~ th~ formula (OC~12-CH2?p~--R1 o ~
.j .
,,,, ; ,: . ' . ' .
l-t8712/A
Process for printin~ and photochemically stabilisin~ polyester fibre materials The present invention relates to a process for printing and photochemically stabilising polyester fibre materials with disperse dyes.
Processes for prinhng polyester fibre materials with disperse dyes are known, inter alia from DE-A-3 918 603. The printing inks applied in the process of this patent speci~lcation and the fibre materials are, however, materially damaged by the action of light and simultaneous exposure to heat. In the automotive sector or in the swimwear sector or, for example, in the field of furnishing fabrics, where exacting demands are made of the lighfastness of printing inks and of the photochemical stability of the fibres, it is not possible to use the printed fabrics obtained by this process.
It is therefore the object of this invention to provide a process for printing polyester fabrics, which makes it possible to stabilise polyester fabrics photochemically and to enhance the lightfastness of the printing inks appIied to said ~abrics.
It has now been found that, by using a print paste which contains a UV absorber, on the one hand the fabric is stabilised photochemically and enhanced lightfastness is imparted to the printing inks andj surprisingly, on the other, that markedly better colour yields are also obtained.
.
The invention accordingly provides a process for printing and photochemically stabilising polyester fibre materials with disperse dyes and subsequendy subjecting the materials to a heat treatment, which process comprises printing said materials with an aqueous print paste which, in addition to the disperse dye, contains a UV absorber.
UV Absorbers suitable for the inventive process are those which are resistant tosublimation at temperatures up to 165C.
The UV absorbers present in the print paste are suitably compounds of the class of the hydroxyphenyl-s-triazines which have the formula 2~73~
2 1~89-8~g7 ~OH
~1) .
N~N
11 .
P(1 N R2 whereln R is Cl-Csalkyl, Cl-CsaLkoxy, halogen~ hydroxy, l and R~ are each independently of the other Cl-Cl8aL~cyl, Cl-CI8alkyl which issubstituted ~y hydroxy, Cl-Csalkoxy, Cl-C~jalkylthio7 amino or Cl-Cs-mono- or Cl-C5-dialkylarnino, phenyl or phenyl which is substituted by chloro, hydroxy, Cl-CsaL~yl and/or Cl-CI2aL~oxy, or a rad;cal of fonnula ( 0 C H 2 - C H 2 ) p O -~R
n isO,lor2, p is 1 to 5 and R3 is hydrogen or Cl-Csalkyl.
::
R, R~ 2 and R3 as alkyl may be straight-chain or branched and are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-bu~yl, tert-butyl, pentyl, isopen~yl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isonony1, n-dodecyl, heptadecyl or oetadecyl.
Cl-C:sAlkoxy or Cl-Csalkylthio may be me~oxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, rnethylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio or tert-pentylthio.
Examples for mono-Cl-CsaLkylamino are monomethyl-, monoethyl-, monopropyl-, monoisopropyl-, monobutyl- or monopentylamino. Examples for di-CI-C5alkylamino are dimethyl-, methylethyl- or diethylamino.
21~8g-8497 3 2~73~8~
H~108en w~ll bo ~on t¢ moaA fluoro, bromo or, pre~rably, chloro. ~ ., Importarlt ~-lsiazine~ are those of fonnula .
a OH
N N
` ~ J~NJ~RB
.. . . .
wherein R ig hydrogcn or has ~he meaning glvel~ ~n fonnula(l), ~nd R~ and Rs ~ each indopendently of lho other un~ubst~tuted phenyl or phenyl subs~nlted by Cl-Csalkyt ~nd/or Cl-Csallcoxy, p: is l to S, and R6 ~8 hyd~ogen or C~ 5alkyl.
: . Other p~ifcmid ~iszlne~ ~ Ihoso of ~osmula (3) ~OH
N
whercin ~7 i~ Cl-Cs~kyl or C1 -C5alkoxy, R~ ~nd R~ are eacll independently of tho other unsubstitu~ed phenyl or phcnyl bslltulcdby Cl-CsalkylandlorCI-C5alkoxy or a radiral o~ th~ formula (OC~12-CH2?p~--R1 o ~
.j .
,,,, ; ,: . ' . ' .
4 2~73~
Pl is 1 to 3, and Rlo is methyl or ethyl.
Compounds of particular interest are those wherein R7 is Cl-CsaLtcoxy, and R~ and Rg are each are each independently of the other tolyl or xylyl phenyl.
Further preferred UV absorbers of formula (3) are those wherein R7 is Cl-C5alkoxy, and R8 and Rg are each phenyl.
Exemplary of suitable compounds of formulae (1), (2) and (3) are:
2-(2'-hydroxy-5'-methylphenyl)-4,6-dimethyl-s-triazine; m.p. 131C:
2-(2'-hydroxy-3',5'-dimethylphenyl)-4,6-dimethyl-s-triazine: m.p. 177C:
2-(2'-hydroxy-4',5'-dimethylphenyl)-4,6-dimethyl-s-tIiazine: ~ 349 ~m: T 48 %:
2-(2'-hydroxy-4',5'-dimethylphenyl)-4,6-diethyl-s-triazine: m.p. 98C:
2-(2'-hydroxy-5'-chlorophenyl)-4,6-dimethyl-s-triazine: m.p. 160C:
2-(2'-hydroxyphenyl)-4,6-dimethyl-s-triazine: m.p. 133C:
2-(2'-hydroxy-5'-tert-butylphenyl)-4,6-dimethyl-s-triazine: ~ 352 llm: I' 60 %:
2-(2'-hydroxyphenyl)-4,6-didecyl-s-tliazine: m.p.53C:
2-(2'-hydroxyphenyl)-4,6-dinonyl-s-triazine: m.p. 45C.
2-(2'-hydroxyphenyl)-4,6-diheptadecyl-s-triazine: ~ 338 ~,lm: T 80 %:
2-(2'-hydroxyphenyl)-4,6-dipropyl-s-triazine: m.p. 18 to 20C:
2-(2'-hydroxyphenyl)-4,6-bis(~-methylmercaptoethyl)-s-triazine: ~ 34111m: T 60 %:
2-(2'-hydroxyphenyl)-4,6-bis(B-dimethylaminoethyl)-s-triazine: ~ 34011m: T 63 %:2-(2'-hydroxyphenyl)-4,6-bis-(B-butylaminoethyl)-s-triazine: ~ 341 llm: T 66 %:
2-(2'-hydroxyphenyl)-4,6-di-tert-butyl-s-triazine: ~ 338 ~,lm: T 68 %:
2-(2'-hydroxyphenyl)-4,6-dioctyl-s-triazine: m.p. 40C:
2-(2'-hydroxy-4'-methoxyphenyl)-4,6-diphenyl-s-triazine: m.p. 204-205C
2-(2'-hydroxy-4'-ethoxyphenyl)-4,6-diphenyl-s-triazine: m.p. 201-202C and 2-(2'-hydroxy-4 ' -isopropyl)~4,6-diphenyl-s-triazine: m .p. 181 - 182C.
4,6-bis(2-hydroxy-4-methoxyphenyl)-2-(2-propoxyethoxy)-1,3,5-triazine 4,6-bis(2-hydroxy-4-propoxyphenyl)-2-(2-methoxyethoxy)-1,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-(2-methoxyethoxy)- l ,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-(2-methoxyethoxy)- 1,3,5 -~iazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-(2-ethoxyethoxy)- 1,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-[2-(2-ethoxyethoxy)ethoxy]- 1,3,5-triazine 2~73~0 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-(2-ethoxyethoxy)- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-[2-(2-ethoxyethoxy)ethoxy]- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl~-2-(2-ethoxy-2-methylethoxy)- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-(ethoxymethoxy)-1 ,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-octyloxy- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl~-2-{2-[2-(2-ethoxy)ethoxy]ethoxy~ethoxy-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-{2-[2-(2-ethoxy)ethoxy]ethoxy}ethoxy-1,3,5-tria-zine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-butoxy-1,3,5-triazine (T = percentage ~ansmission of a solution of 1 mg of substance in 100 ml of chloroform at a layer thickness of 1 cm; ~ [~m] is the maximum coefficient of extinction).
A further UV absorber eligible for use in the print pastes is a compound of the class of the benzotriazoles of formula OH X
(4) ¢~ N
wherein one of the substituents Xl and X2 is hydrogen aDd the other substituent of Xl and X2 is hydrogen or Cl-Csalkyl, Cl-Csalkoxy or halogen or the group ~R
-CH2-N~
CO-(O)m l Rl2 in which Rll is hydrogen, Cl-ClOalkyl, Cs-C8cycloalkyl, C7-ClOaralkyl or C6-ClOaryl, Rl2 is hydrogen, Cl-C20alkyl, C2-CI7alkenyl, Cs-C8cycloalkyl, C7-ClOaralkyl, (~8-CloaralkenYl or C6-ClOaryl, and m is 1 or 2, and if m = 1, 2073~80 Rll and Rl2, together with the ring linking group -N-CO-, may also forrn a mononwcle~r or polynuclear nitrogen-containing heterocycle and, in this case Rll is -CO- or unsubstituted methylene or Cl-Csalkyl-substituted methylene, and Rl2 is C2-C5alkylene, C2-C5alkenylene, C6-ClOarylene or vicinally bound di-, tetra- or hexahydro-C6-ClOarylene, X3 is Cl-CsaLIcyl, Cl-Csalkoxy, halogen, C6-ClOaryl, C7-ClOaralkyl or Cs-C8cycloalkyl, the ring A may be substituted in positions 1, 2 and 3 by Cl-Csalkyl, Cl-CsaLkoxy, carboxy, Cl-Csalkoxycarbonyl, H2NCO-, S~)2-, Cl-Csalkylsulfonyl or halogen.
The substituents Rl 1 and Rl2 defined as Cl-ClOalkyl and Cl-C20alkyl, respectively, may be straight-chain or branched and are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, n-dodecyl, heptadecyl, octadecyl or icosyl.
Rll and Rl2 as C6-ClOaryl may be a mono- or bicyclic aromatic radical such as phenyl or naphthyl.
Rll and Rl2 as C7-ClOaraLIcyl rnay be benzyl, phenethyl, a-methylphenethyl or a,a-dimethylbenzyl.
Rll and Rl2 as Cs-C8cycloalkyl may be cyclopentyl, cyclohexyl, cycloheptyl or cyclooc.S~l.
Rl2 as C2-Cl7aL1cenyl may typically be ~inyl, allyl, l-propenyl~ 2-butenyl, 2-pentenyl, 2-hexenyl, 2-decenyl, 3,6,8-decatrienyl or 2-heptadecenyl.
Rl2 as Cg-ClOaralkenyl may be styryl or cinnamyl.
If Rll and Rl2 are linked together and Rll is the member -CO-, then the meaning of Rl2 is - as C2-Csalkylene:
ethylene, trimethylene or tetramethylene to form the nitrogen-containing heterocycles 2,5-dioxopy~Tolidine, 2,6-dioxopiperidine and 2,7-dioxoazacycloheptane, - as C2-Csalkenylene:
2073~80 vinylene, propenylene or butenylene to form the heterocycle 2,5-dioxo-~3-pyIroline or 2,3,G,7-tetrahydro- lH-azepine-2,7-dione;
- as C6-Cl0arylene:
o-phenylene or o-naphthylene to form the heterocycles lH-isoindole-1,3(2H)-dione(phthalimide) or 2H-benz[f~isoindole-1,3-dione, or - as di-, tetra- or hexahydro-C6-Cl0arylene:
cyclohexadiene or cyclohexene to forrn the heterocycles 3,4-dihydrophthalimide, 3,4,5,6-tetrahydrophthalimide or 3,4,5,6,8,9-hexahydrophthalimide.
If Rll and Rl2 are linked together and Rll is unsubstituted methylene or Cl-Csalkyl-substituted methylene, then, where Rl2 has the above meanings, corresponding oxo compounds are formed instead of the dioxo compounds.
The print pastes may also contain UV absorbers of the benzophenone series which conform to the formula ~C~
Rl4 wherein R13 is hydrogen, hydroxy, Cl-Cl4alkoxy or phenoxy, and Cl-Cl4aLkoxy can be substituted by a radical of formula ll l 0~ ~ andJor substituted by acyloxy, wherein -8- 2a73~80 Rl4 is hydrogen, halogen or Cl-Csalkyl, Rls is hydrogen, hydroxy or Cl-Csalkoxy, and 6 is hydrogen or hydroxy.
Acyl is Cl-C5alkanoyl, typically formyl, acetyl, propionyl, acryloyl, methacryloyl or benzoyl.
The compounds of fonnulae (1), (2) and (3) are known and can be prepared in a manner known per se, conveniently by heating an amidine and a o-hydroxybenzenecarboxylate, preferably in about the molarratio of 2:1, in boiling organic solvents [cf. US-A-3 896 125 and Helv. Chim. Acta 55, 1566-1595 (1972)].
The compounds of forrnula (5) can be prepared by methods known per se, conveniently as disclosed in US-A-3 468 938, US-A-3 696 077 or US-A-4 698 064.
Some of the compounds of formula (4) are known or are novel compounds. The novelcompounds can be prepared by methods known per se, conveniently by reacting a corresponding 2-(2'-hydroxyphenyl)benzotriazole which is capable of substitution in 3'- or 5'-position with the N-methylol compound of a carbox~nide or urethane (cf.
~J.S. 4 077 971).
The UV absorbers which may suitably be used in the process of this invention are used in the form of aqueous dispersions.
Suitable dispersants for these aqueous dispersions are compounds which are selected from the following compound classes:
(a) acid esters, or their salts, of aLkylene oxide polyadducts of formula (6) ~ O ~alkylene-(~ X
(Y)q wherein ~ is the acid radical of an inorganic oxygen-containing acid such as sulfuric 2~73.580 g acid or, preferably, phosphoric acid, or is also the radical of an organic acid, and Y is Cl-Cl2aL~yl, aryl or aralkyl, "alkylene" is the ethylene or propylene radical, and qis 1 to4andris4to50, (b) polystyrene sulfonates, (c) fatty acid taurides, (d) alkylated diphenyl oxide mono- or disulfonates, (e) sulfonates of polycarboxylates, (f) polyadducts of 1 to 60 mol, preferably 2 to 30 mol, of ethylene oxide ancVorpropylene oxide with fatty amines9 fatty amides, fatty acids or fatty alcohols, each of 8 to 22 carbon atoms or with trihydric to hexahydric alkanols of 3 to 6 carbon atoms, which polyadducts have been converted into an acid ester with an organic dicarboxylic acid or an organic polybasic acid, (g) ligninsulfonates, and (h) forrnaldehyde condensates.
The dispersions may also contain additional components such as nonionic surfactants, other anionic and/or nonionic compounds, commercially available antifoams, preservatives and antifreeze agents.
The dispersions are conveniently prepared by making the UV absorbers of formulae (1), (2), (3), (4) or (5) into a paste with a dispersant~ for example the acid ester of formula (6), and water in a mixer and, after addition of any desired additional components, such as nonionic surfactants, further anionic andlor nonionic compounds, including the antifoam, preservative and antifreeze agent, dispersing the mixture for 1 to 30, preferably 1 to 10, hours. Dispersing is conveniently effected by the action of high shear forces, for example by milling in a ball, sand or bead mill. After milling, an aqueous solution of a commercial stabiliser or thickener and, if desired, further water can be added, and the mixture is stirred until a homogeneous dispersion is obtained.
2~73~
~o -The UV absorbers are added in the form of their aqueous dispersions to the print pastes.
The print paste contains the appropriate UV absorber in a concentration of 0.5 to 8 %, preferably of 1 to 2 %, based on the weight of the print paste.
Fibre materials which are suitable for use in the process of this invention are acid-modified polyester fibres and, preferably, linear polyester fibres. By linear polyester fibres are meant in this context synthetic fibres obtained for example by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis-(hydroxymethyl)cyclohexane and copolymers of terephthalic and isophthalic acid and ethylene glycol. The linear polyester hitherto used almost exclusively in the textile indust~y consists of terephthalic acid and ethylene glycol. Acid-modi~led polyester fibres are typically polycondensates of terephthalic acid or isophthalic acid, ethylene glycol and sodium 3-(1,3- or 2,3-dihydroxypropoxy)propanesulfonate, sodium (2,3-dimethylolbutoxy)propanesulfonate, disodium isopropylidenedibenzeneoxy-propylsulfonate or 3,5--dicarboxybenzenesulfonic acid, sulfonated terephthalic acid, sulfonated 4-methoxybenzenecarboxylic acid or sulfonated biphenyl-4,4'-dicarboxylic acid.
The disperse dyes are water-insoluble or sparingly soluble dyes of different classes, typically nitro dyes, aminoketone dyes, ketoneimine dyes, methine dyes, nitrodiphenyl dyes, quinoline dyes and, preferably, anthraquinone dyes or azo dyes such as monoazo or disazo dyes. It is also possible to use mixtures of different disperse dyes.
It is advantageous, however, not to use the dye (cut or uncut~ by itself, but in the form of an aqueous forrnulation which contains the water-insoluble or spaIingly soluble dye (or dye mixture). Such formulations are preferably those described in DE-OS-2 85û 482.
The amount of dye to be added to the print paste will depend on the desired depth of shade. Amounts of 0.01 to 15 % by weight, preferably of 0.02 to 10 % by weight, based on the weight of the textile material, have been found useful.
In addition to containing the dyes and the aqueous dispersion of UV absorber, the print pastes conveniently contain acid-stable thickeners, preferably of natural origin such as carob bean flour derivatives, especially sodium alginate by itself or in combination with -11- 2~73~80 modified cellulose, preferably with 20 to 25 % by weight of carboxymethyl cellulose. If des*ed~ the print pastes may further contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, chelating agents, emulsifiers, water-insoluble solvents, oxidising agents or deaerating agents.
Particularly suitable preservatives are formaldehyde donors, typically paraformaldehyde and trioxane, preferably c. 30 to 40 % formaldehyde solutions. Suitable chelating agents are sodium nitrilotriacetate, sodium ethylenediaminetetraacetate7 preferably sodium polymethaphosphate, more particularly sodium hexamethaphosphate. Emulsifiers arepreferably polyadducts of an alkylene oxide and a fatty alcohol, more particularly a polyaduct of oleyl alcohol and ethylene oxide. Water-insoluble solvents are preferably high-boiling saturated hydrocarbons, more particularly paraffins having a boiling range from about 160 to 210C (white spirits~. Oxidising agents aTe typically aromatic nitro compounds, preferably an aromatic mono- or dinitrocarboxylic or mono- or dinitrosulfonic acid which may be in the form of an alkylene oxide polyadduct, preferably a nitrobenænesulfonic acid. Deaerating agents are suitably high-boiling solvents, preferably terpentine oils, higher alcohols, preferably C8-ClOalcohols, terpene alcohols or deaerating agents based on mineral and/or silicone oils, especially commercial formulationscomprising about 15-25 ~b by weight of a mixture of mineral and silicone oils and about 75-85 % by weight of a C~alcohol such as 2-ethyl-n-hexanol.
For printing the fibre materials, the print paste is applied direct to the whole or part of the surface, conveniently using printing machines of conventional construction, typically rotogravure, rotary screen printing and surface screen printing machines.
The fibre material is dried after printing in the temperature range up to 150C, preferably in thc range from 80 to 120C.
The subsequent fixation of the fibre material is usually carried out by dry heat(thermofixation) or with superheated steam under atmospheric pressure (HT fixation).
Fixation is carried out under the following conditions:
HT fixation: 4 to 8 minutes at 170 to 180C
thermo~lxation: 1 to 2 minutes at 200 to 230C.
The prints are finished in conventional manner by washing off with water, followed by an -12- 2073~89 optional reductive afterclear in alkaline medium, conveniently with sodium dithionite. In this last mentioned case, the prints are again washed off and dried.
The process of this invention is also suitable for transfer printing. For this utility the print paste is applied to the entire surface of the support, preferably patterned, using prin~ing machines of conventional construction, such as rotary screen and, most preferably, rotogravure machines.
The support used in transfer printing is conveniently a flexible, preferably dimensionally stable ribbon, strip or sheet with a smooth surface. The support must be heat stable and inert, i.e. have no affinity for the different components of the print paste. It may be made of different materials, typically metal, such as an aluminium or steel sheet, plastic, paper or a planar textile material, which supports may be coated with a film of vinyl resin, ethyl cellulose or polyurethane resin. For cost reasons, paper is principally used.
After applying the print paste, the printed support is dried for about S to 20 seconds at about 80-150C, preferably at 80-120C. The actual transfer printing is carried out on a press batchwise or in a transfer printing unit continuously at 160-2S0C, preferably 1~0-220C. The contact time is dependent on the temperature and is in the range from 20 to 60, preferably 30 to 45, seconds at 230C and under pressure, whereupon the dye transfers from the support on to the ~lbre material.
Upon terrnination of the heat and pressure treatment, the printed f1bre material is removed from the support. Norrnally neither an aftertreatment, i.e. a steam treatment, is necessary to f1x the dye, nor a washing off step to improve the fastness properties.
The inventive process makes it possible to obtain on the fabric strong, wash- and rubfast prints with a good white ground. The prints are distinguished by superior lightfastness and the fibre material is photochemically stable.
In the following Example parts and percentages are by weight, unless otherwise indicated.
Example 1: A polyester automotive upholstery fabric is printed with a print paste which is prepared as follows:
750 parts of a stock thickening containing per 1000 parts 2~73~0 9 parts of thickener, e.g. a starch ether 18 parts of thickener, e.g. a sodium alginate 3.75 parts of sodium dihydrogen phosphate 2.48 parts of sodium chlorate, and 716.77 parts of water are mixed with parts of a commercial formulation of a dye of formula (I) ~OCHa O HN--S02~ CH3 parts of a formulation comprising parts of the UV absorber of formula (101) N~N
, e3 8.5 parts of the reaction product, neutralised with triethanolamine, of phosphorus pentoxide with the polyadduct (18 EO units) of ethylene oxide with 2.S to 3 mol of styrene and 1 mol of phenol, 2.0 parts of N,N'-ethylenebis(stearamide) 0.3 parts of a biopolymer based on polysaccharide and 2~73~80 145 par~s of water.
The upholstery fabric is printed with this print paste on a printing table, diied, and then treated at 180C with superheated steam. The fabric is subsequently washed with cold water and given a reductive afterclear wit'n 2 gll of sodium hydroxide solution (30 %) 2 g/l of sodium dithionite, and g/l of a commercial detergent at 60 to 70C. The fabric is then washed with warm (60C) and cold water and dried.
A full red print with a good white ground and good end-use properties such as fas~ness to light, washing and rubbing, is obtained.
Example 2: l~e procedure of Exarnple 1 is repeated, but replacing 25 parts of the UV absorber of formula (101) with 25 parts of the UV absorber of formula O OH OH O
Il I l 11 (102) ~ ~2C/ ~ /~
o=l--C=CH2 Example 3: The procedure of Example 1 is repeated, but replacing 25 parts of theUV absorber of forrnula (101) with 25 parts of the UV absorber of formula O OH
(103) ~-OH
2~17~80 Example 4: The procedure of Example 1 is repeated, but replacing 25 parts of the UV absorber of formula (101) wi~h 25 parts of the UV absorber of -formula \\
Examples 5-12: The procedure of Example 1 is repeated, but replacing 25 parts of the UY absorber of forrnula (101) with 25 parts of each of the following UV absorbers:
~OH
(105) J~
N~ N
,~1~N
2~73~8~
~OH
(106) J~, CH3 N ~ N CH3 ~N
~OH
(107) N~N OH
~1N~ ~O-CH3 ' ~
~OH
(108) J~
N~ N
~N ~ CH3 - 17- 2~73~8~
HO N ~ N HO
H3C O~N ~ o-cH3 O-cH2-cH2-o-cH2-cH2-c~l3 HO N~N HO
H3C-Ol ~O CH3 O-CH2-CH2-O-cH3 :~ HO N~N HO
HsC~-O~N~O-C2Hs O-cH2-cH2-cH2-c~3 HO N~ ~N HO
HsC2O N~\O-C2H5 A transfer paper is printed with a print paste which is prepared as follows:
600 parts of a stock thickening containing per 1000 parts 24.5 parts of a thickener based on polyacrylic acid, - 18- 2~3 3.15 parts of 30 % aqueous sodium hydroxide 4.2 parts of a deaerating agent based on 2-ethyl-n-hexanol parts of a polyvinyl alcohol, and 498.15 parts of water are mixed with 100 parts of a commercial forrnulation of a dye of formula (I), 200 parts of an aqueous formulation comprising 50 parts of the UV absorber of forrnula (101) 17 parts of the reaction product, neutralised with triethanolamine, of phosphorus pentoxide with the polyadduc~ (18 EO units) of ethylene oxide with 2.5 to 3 mol of styrene and 1 mol of phenol, 4.0 parts of N,N'-ethylenebis(stearamide) 0.6 part of a biopolymer based on polysaccharide and 100 parts of water.
The dye is transferred by heating the pnnted transfer paper for 60 seconds at 230C.
A strong patterned print of good levelness, good fastness properties and with sharp contours is obtained.
Example 14: The procedure of Example 13 is repeated, except ~at ~he UV absorber is padded on to the fabric in arnounts of 1 to 4 % by weight before prin~ing. The paper is printed simultaneously with a print paste which contains no UV absorber. In the course of the transfer printing, the dye is transferred from the paper to the textile fabric and simultaneously fixed with the UV absorber.
A strong patterned print of good levelness, good fastness properties and with sharp contours is obtained on a white ground on the polyester fabric.
Pl is 1 to 3, and Rlo is methyl or ethyl.
Compounds of particular interest are those wherein R7 is Cl-CsaLtcoxy, and R~ and Rg are each are each independently of the other tolyl or xylyl phenyl.
Further preferred UV absorbers of formula (3) are those wherein R7 is Cl-C5alkoxy, and R8 and Rg are each phenyl.
Exemplary of suitable compounds of formulae (1), (2) and (3) are:
2-(2'-hydroxy-5'-methylphenyl)-4,6-dimethyl-s-triazine; m.p. 131C:
2-(2'-hydroxy-3',5'-dimethylphenyl)-4,6-dimethyl-s-triazine: m.p. 177C:
2-(2'-hydroxy-4',5'-dimethylphenyl)-4,6-dimethyl-s-tIiazine: ~ 349 ~m: T 48 %:
2-(2'-hydroxy-4',5'-dimethylphenyl)-4,6-diethyl-s-triazine: m.p. 98C:
2-(2'-hydroxy-5'-chlorophenyl)-4,6-dimethyl-s-triazine: m.p. 160C:
2-(2'-hydroxyphenyl)-4,6-dimethyl-s-triazine: m.p. 133C:
2-(2'-hydroxy-5'-tert-butylphenyl)-4,6-dimethyl-s-triazine: ~ 352 llm: I' 60 %:
2-(2'-hydroxyphenyl)-4,6-didecyl-s-tliazine: m.p.53C:
2-(2'-hydroxyphenyl)-4,6-dinonyl-s-triazine: m.p. 45C.
2-(2'-hydroxyphenyl)-4,6-diheptadecyl-s-triazine: ~ 338 ~,lm: T 80 %:
2-(2'-hydroxyphenyl)-4,6-dipropyl-s-triazine: m.p. 18 to 20C:
2-(2'-hydroxyphenyl)-4,6-bis(~-methylmercaptoethyl)-s-triazine: ~ 34111m: T 60 %:
2-(2'-hydroxyphenyl)-4,6-bis(B-dimethylaminoethyl)-s-triazine: ~ 34011m: T 63 %:2-(2'-hydroxyphenyl)-4,6-bis-(B-butylaminoethyl)-s-triazine: ~ 341 llm: T 66 %:
2-(2'-hydroxyphenyl)-4,6-di-tert-butyl-s-triazine: ~ 338 ~,lm: T 68 %:
2-(2'-hydroxyphenyl)-4,6-dioctyl-s-triazine: m.p. 40C:
2-(2'-hydroxy-4'-methoxyphenyl)-4,6-diphenyl-s-triazine: m.p. 204-205C
2-(2'-hydroxy-4'-ethoxyphenyl)-4,6-diphenyl-s-triazine: m.p. 201-202C and 2-(2'-hydroxy-4 ' -isopropyl)~4,6-diphenyl-s-triazine: m .p. 181 - 182C.
4,6-bis(2-hydroxy-4-methoxyphenyl)-2-(2-propoxyethoxy)-1,3,5-triazine 4,6-bis(2-hydroxy-4-propoxyphenyl)-2-(2-methoxyethoxy)-1,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-(2-methoxyethoxy)- l ,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-(2-methoxyethoxy)- 1,3,5 -~iazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-(2-ethoxyethoxy)- 1,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-[2-(2-ethoxyethoxy)ethoxy]- 1,3,5-triazine 2~73~0 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-(2-ethoxyethoxy)- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-[2-(2-ethoxyethoxy)ethoxy]- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl~-2-(2-ethoxy-2-methylethoxy)- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-(ethoxymethoxy)-1 ,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl)-2-octyloxy- 1 ,3,5-triazine 4,6-bis(2-hydroxy-4-methoxyphenyl~-2-{2-[2-(2-ethoxy)ethoxy]ethoxy~ethoxy-triazine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-{2-[2-(2-ethoxy)ethoxy]ethoxy}ethoxy-1,3,5-tria-zine 4,6-bis(2-hydroxy-4-ethoxyphenyl)-2-butoxy-1,3,5-triazine (T = percentage ~ansmission of a solution of 1 mg of substance in 100 ml of chloroform at a layer thickness of 1 cm; ~ [~m] is the maximum coefficient of extinction).
A further UV absorber eligible for use in the print pastes is a compound of the class of the benzotriazoles of formula OH X
(4) ¢~ N
wherein one of the substituents Xl and X2 is hydrogen aDd the other substituent of Xl and X2 is hydrogen or Cl-Csalkyl, Cl-Csalkoxy or halogen or the group ~R
-CH2-N~
CO-(O)m l Rl2 in which Rll is hydrogen, Cl-ClOalkyl, Cs-C8cycloalkyl, C7-ClOaralkyl or C6-ClOaryl, Rl2 is hydrogen, Cl-C20alkyl, C2-CI7alkenyl, Cs-C8cycloalkyl, C7-ClOaralkyl, (~8-CloaralkenYl or C6-ClOaryl, and m is 1 or 2, and if m = 1, 2073~80 Rll and Rl2, together with the ring linking group -N-CO-, may also forrn a mononwcle~r or polynuclear nitrogen-containing heterocycle and, in this case Rll is -CO- or unsubstituted methylene or Cl-Csalkyl-substituted methylene, and Rl2 is C2-C5alkylene, C2-C5alkenylene, C6-ClOarylene or vicinally bound di-, tetra- or hexahydro-C6-ClOarylene, X3 is Cl-CsaLIcyl, Cl-Csalkoxy, halogen, C6-ClOaryl, C7-ClOaralkyl or Cs-C8cycloalkyl, the ring A may be substituted in positions 1, 2 and 3 by Cl-Csalkyl, Cl-CsaLkoxy, carboxy, Cl-Csalkoxycarbonyl, H2NCO-, S~)2-, Cl-Csalkylsulfonyl or halogen.
The substituents Rl 1 and Rl2 defined as Cl-ClOalkyl and Cl-C20alkyl, respectively, may be straight-chain or branched and are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, n-dodecyl, heptadecyl, octadecyl or icosyl.
Rll and Rl2 as C6-ClOaryl may be a mono- or bicyclic aromatic radical such as phenyl or naphthyl.
Rll and Rl2 as C7-ClOaraLIcyl rnay be benzyl, phenethyl, a-methylphenethyl or a,a-dimethylbenzyl.
Rll and Rl2 as Cs-C8cycloalkyl may be cyclopentyl, cyclohexyl, cycloheptyl or cyclooc.S~l.
Rl2 as C2-Cl7aL1cenyl may typically be ~inyl, allyl, l-propenyl~ 2-butenyl, 2-pentenyl, 2-hexenyl, 2-decenyl, 3,6,8-decatrienyl or 2-heptadecenyl.
Rl2 as Cg-ClOaralkenyl may be styryl or cinnamyl.
If Rll and Rl2 are linked together and Rll is the member -CO-, then the meaning of Rl2 is - as C2-Csalkylene:
ethylene, trimethylene or tetramethylene to form the nitrogen-containing heterocycles 2,5-dioxopy~Tolidine, 2,6-dioxopiperidine and 2,7-dioxoazacycloheptane, - as C2-Csalkenylene:
2073~80 vinylene, propenylene or butenylene to form the heterocycle 2,5-dioxo-~3-pyIroline or 2,3,G,7-tetrahydro- lH-azepine-2,7-dione;
- as C6-Cl0arylene:
o-phenylene or o-naphthylene to form the heterocycles lH-isoindole-1,3(2H)-dione(phthalimide) or 2H-benz[f~isoindole-1,3-dione, or - as di-, tetra- or hexahydro-C6-Cl0arylene:
cyclohexadiene or cyclohexene to forrn the heterocycles 3,4-dihydrophthalimide, 3,4,5,6-tetrahydrophthalimide or 3,4,5,6,8,9-hexahydrophthalimide.
If Rll and Rl2 are linked together and Rll is unsubstituted methylene or Cl-Csalkyl-substituted methylene, then, where Rl2 has the above meanings, corresponding oxo compounds are formed instead of the dioxo compounds.
The print pastes may also contain UV absorbers of the benzophenone series which conform to the formula ~C~
Rl4 wherein R13 is hydrogen, hydroxy, Cl-Cl4alkoxy or phenoxy, and Cl-Cl4aLkoxy can be substituted by a radical of formula ll l 0~ ~ andJor substituted by acyloxy, wherein -8- 2a73~80 Rl4 is hydrogen, halogen or Cl-Csalkyl, Rls is hydrogen, hydroxy or Cl-Csalkoxy, and 6 is hydrogen or hydroxy.
Acyl is Cl-C5alkanoyl, typically formyl, acetyl, propionyl, acryloyl, methacryloyl or benzoyl.
The compounds of fonnulae (1), (2) and (3) are known and can be prepared in a manner known per se, conveniently by heating an amidine and a o-hydroxybenzenecarboxylate, preferably in about the molarratio of 2:1, in boiling organic solvents [cf. US-A-3 896 125 and Helv. Chim. Acta 55, 1566-1595 (1972)].
The compounds of forrnula (5) can be prepared by methods known per se, conveniently as disclosed in US-A-3 468 938, US-A-3 696 077 or US-A-4 698 064.
Some of the compounds of formula (4) are known or are novel compounds. The novelcompounds can be prepared by methods known per se, conveniently by reacting a corresponding 2-(2'-hydroxyphenyl)benzotriazole which is capable of substitution in 3'- or 5'-position with the N-methylol compound of a carbox~nide or urethane (cf.
~J.S. 4 077 971).
The UV absorbers which may suitably be used in the process of this invention are used in the form of aqueous dispersions.
Suitable dispersants for these aqueous dispersions are compounds which are selected from the following compound classes:
(a) acid esters, or their salts, of aLkylene oxide polyadducts of formula (6) ~ O ~alkylene-(~ X
(Y)q wherein ~ is the acid radical of an inorganic oxygen-containing acid such as sulfuric 2~73.580 g acid or, preferably, phosphoric acid, or is also the radical of an organic acid, and Y is Cl-Cl2aL~yl, aryl or aralkyl, "alkylene" is the ethylene or propylene radical, and qis 1 to4andris4to50, (b) polystyrene sulfonates, (c) fatty acid taurides, (d) alkylated diphenyl oxide mono- or disulfonates, (e) sulfonates of polycarboxylates, (f) polyadducts of 1 to 60 mol, preferably 2 to 30 mol, of ethylene oxide ancVorpropylene oxide with fatty amines9 fatty amides, fatty acids or fatty alcohols, each of 8 to 22 carbon atoms or with trihydric to hexahydric alkanols of 3 to 6 carbon atoms, which polyadducts have been converted into an acid ester with an organic dicarboxylic acid or an organic polybasic acid, (g) ligninsulfonates, and (h) forrnaldehyde condensates.
The dispersions may also contain additional components such as nonionic surfactants, other anionic and/or nonionic compounds, commercially available antifoams, preservatives and antifreeze agents.
The dispersions are conveniently prepared by making the UV absorbers of formulae (1), (2), (3), (4) or (5) into a paste with a dispersant~ for example the acid ester of formula (6), and water in a mixer and, after addition of any desired additional components, such as nonionic surfactants, further anionic andlor nonionic compounds, including the antifoam, preservative and antifreeze agent, dispersing the mixture for 1 to 30, preferably 1 to 10, hours. Dispersing is conveniently effected by the action of high shear forces, for example by milling in a ball, sand or bead mill. After milling, an aqueous solution of a commercial stabiliser or thickener and, if desired, further water can be added, and the mixture is stirred until a homogeneous dispersion is obtained.
2~73~
~o -The UV absorbers are added in the form of their aqueous dispersions to the print pastes.
The print paste contains the appropriate UV absorber in a concentration of 0.5 to 8 %, preferably of 1 to 2 %, based on the weight of the print paste.
Fibre materials which are suitable for use in the process of this invention are acid-modified polyester fibres and, preferably, linear polyester fibres. By linear polyester fibres are meant in this context synthetic fibres obtained for example by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis-(hydroxymethyl)cyclohexane and copolymers of terephthalic and isophthalic acid and ethylene glycol. The linear polyester hitherto used almost exclusively in the textile indust~y consists of terephthalic acid and ethylene glycol. Acid-modi~led polyester fibres are typically polycondensates of terephthalic acid or isophthalic acid, ethylene glycol and sodium 3-(1,3- or 2,3-dihydroxypropoxy)propanesulfonate, sodium (2,3-dimethylolbutoxy)propanesulfonate, disodium isopropylidenedibenzeneoxy-propylsulfonate or 3,5--dicarboxybenzenesulfonic acid, sulfonated terephthalic acid, sulfonated 4-methoxybenzenecarboxylic acid or sulfonated biphenyl-4,4'-dicarboxylic acid.
The disperse dyes are water-insoluble or sparingly soluble dyes of different classes, typically nitro dyes, aminoketone dyes, ketoneimine dyes, methine dyes, nitrodiphenyl dyes, quinoline dyes and, preferably, anthraquinone dyes or azo dyes such as monoazo or disazo dyes. It is also possible to use mixtures of different disperse dyes.
It is advantageous, however, not to use the dye (cut or uncut~ by itself, but in the form of an aqueous forrnulation which contains the water-insoluble or spaIingly soluble dye (or dye mixture). Such formulations are preferably those described in DE-OS-2 85û 482.
The amount of dye to be added to the print paste will depend on the desired depth of shade. Amounts of 0.01 to 15 % by weight, preferably of 0.02 to 10 % by weight, based on the weight of the textile material, have been found useful.
In addition to containing the dyes and the aqueous dispersion of UV absorber, the print pastes conveniently contain acid-stable thickeners, preferably of natural origin such as carob bean flour derivatives, especially sodium alginate by itself or in combination with -11- 2~73~80 modified cellulose, preferably with 20 to 25 % by weight of carboxymethyl cellulose. If des*ed~ the print pastes may further contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, chelating agents, emulsifiers, water-insoluble solvents, oxidising agents or deaerating agents.
Particularly suitable preservatives are formaldehyde donors, typically paraformaldehyde and trioxane, preferably c. 30 to 40 % formaldehyde solutions. Suitable chelating agents are sodium nitrilotriacetate, sodium ethylenediaminetetraacetate7 preferably sodium polymethaphosphate, more particularly sodium hexamethaphosphate. Emulsifiers arepreferably polyadducts of an alkylene oxide and a fatty alcohol, more particularly a polyaduct of oleyl alcohol and ethylene oxide. Water-insoluble solvents are preferably high-boiling saturated hydrocarbons, more particularly paraffins having a boiling range from about 160 to 210C (white spirits~. Oxidising agents aTe typically aromatic nitro compounds, preferably an aromatic mono- or dinitrocarboxylic or mono- or dinitrosulfonic acid which may be in the form of an alkylene oxide polyadduct, preferably a nitrobenænesulfonic acid. Deaerating agents are suitably high-boiling solvents, preferably terpentine oils, higher alcohols, preferably C8-ClOalcohols, terpene alcohols or deaerating agents based on mineral and/or silicone oils, especially commercial formulationscomprising about 15-25 ~b by weight of a mixture of mineral and silicone oils and about 75-85 % by weight of a C~alcohol such as 2-ethyl-n-hexanol.
For printing the fibre materials, the print paste is applied direct to the whole or part of the surface, conveniently using printing machines of conventional construction, typically rotogravure, rotary screen printing and surface screen printing machines.
The fibre material is dried after printing in the temperature range up to 150C, preferably in thc range from 80 to 120C.
The subsequent fixation of the fibre material is usually carried out by dry heat(thermofixation) or with superheated steam under atmospheric pressure (HT fixation).
Fixation is carried out under the following conditions:
HT fixation: 4 to 8 minutes at 170 to 180C
thermo~lxation: 1 to 2 minutes at 200 to 230C.
The prints are finished in conventional manner by washing off with water, followed by an -12- 2073~89 optional reductive afterclear in alkaline medium, conveniently with sodium dithionite. In this last mentioned case, the prints are again washed off and dried.
The process of this invention is also suitable for transfer printing. For this utility the print paste is applied to the entire surface of the support, preferably patterned, using prin~ing machines of conventional construction, such as rotary screen and, most preferably, rotogravure machines.
The support used in transfer printing is conveniently a flexible, preferably dimensionally stable ribbon, strip or sheet with a smooth surface. The support must be heat stable and inert, i.e. have no affinity for the different components of the print paste. It may be made of different materials, typically metal, such as an aluminium or steel sheet, plastic, paper or a planar textile material, which supports may be coated with a film of vinyl resin, ethyl cellulose or polyurethane resin. For cost reasons, paper is principally used.
After applying the print paste, the printed support is dried for about S to 20 seconds at about 80-150C, preferably at 80-120C. The actual transfer printing is carried out on a press batchwise or in a transfer printing unit continuously at 160-2S0C, preferably 1~0-220C. The contact time is dependent on the temperature and is in the range from 20 to 60, preferably 30 to 45, seconds at 230C and under pressure, whereupon the dye transfers from the support on to the ~lbre material.
Upon terrnination of the heat and pressure treatment, the printed f1bre material is removed from the support. Norrnally neither an aftertreatment, i.e. a steam treatment, is necessary to f1x the dye, nor a washing off step to improve the fastness properties.
The inventive process makes it possible to obtain on the fabric strong, wash- and rubfast prints with a good white ground. The prints are distinguished by superior lightfastness and the fibre material is photochemically stable.
In the following Example parts and percentages are by weight, unless otherwise indicated.
Example 1: A polyester automotive upholstery fabric is printed with a print paste which is prepared as follows:
750 parts of a stock thickening containing per 1000 parts 2~73~0 9 parts of thickener, e.g. a starch ether 18 parts of thickener, e.g. a sodium alginate 3.75 parts of sodium dihydrogen phosphate 2.48 parts of sodium chlorate, and 716.77 parts of water are mixed with parts of a commercial formulation of a dye of formula (I) ~OCHa O HN--S02~ CH3 parts of a formulation comprising parts of the UV absorber of formula (101) N~N
, e3 8.5 parts of the reaction product, neutralised with triethanolamine, of phosphorus pentoxide with the polyadduct (18 EO units) of ethylene oxide with 2.S to 3 mol of styrene and 1 mol of phenol, 2.0 parts of N,N'-ethylenebis(stearamide) 0.3 parts of a biopolymer based on polysaccharide and 2~73~80 145 par~s of water.
The upholstery fabric is printed with this print paste on a printing table, diied, and then treated at 180C with superheated steam. The fabric is subsequently washed with cold water and given a reductive afterclear wit'n 2 gll of sodium hydroxide solution (30 %) 2 g/l of sodium dithionite, and g/l of a commercial detergent at 60 to 70C. The fabric is then washed with warm (60C) and cold water and dried.
A full red print with a good white ground and good end-use properties such as fas~ness to light, washing and rubbing, is obtained.
Example 2: l~e procedure of Exarnple 1 is repeated, but replacing 25 parts of the UV absorber of formula (101) with 25 parts of the UV absorber of formula O OH OH O
Il I l 11 (102) ~ ~2C/ ~ /~
o=l--C=CH2 Example 3: The procedure of Example 1 is repeated, but replacing 25 parts of theUV absorber of forrnula (101) with 25 parts of the UV absorber of formula O OH
(103) ~-OH
2~17~80 Example 4: The procedure of Example 1 is repeated, but replacing 25 parts of the UV absorber of formula (101) wi~h 25 parts of the UV absorber of -formula \\
Examples 5-12: The procedure of Example 1 is repeated, but replacing 25 parts of the UY absorber of forrnula (101) with 25 parts of each of the following UV absorbers:
~OH
(105) J~
N~ N
,~1~N
2~73~8~
~OH
(106) J~, CH3 N ~ N CH3 ~N
~OH
(107) N~N OH
~1N~ ~O-CH3 ' ~
~OH
(108) J~
N~ N
~N ~ CH3 - 17- 2~73~8~
HO N ~ N HO
H3C O~N ~ o-cH3 O-cH2-cH2-o-cH2-cH2-c~l3 HO N~N HO
H3C-Ol ~O CH3 O-CH2-CH2-O-cH3 :~ HO N~N HO
HsC~-O~N~O-C2Hs O-cH2-cH2-cH2-c~3 HO N~ ~N HO
HsC2O N~\O-C2H5 A transfer paper is printed with a print paste which is prepared as follows:
600 parts of a stock thickening containing per 1000 parts 24.5 parts of a thickener based on polyacrylic acid, - 18- 2~3 3.15 parts of 30 % aqueous sodium hydroxide 4.2 parts of a deaerating agent based on 2-ethyl-n-hexanol parts of a polyvinyl alcohol, and 498.15 parts of water are mixed with 100 parts of a commercial forrnulation of a dye of formula (I), 200 parts of an aqueous formulation comprising 50 parts of the UV absorber of forrnula (101) 17 parts of the reaction product, neutralised with triethanolamine, of phosphorus pentoxide with the polyadduc~ (18 EO units) of ethylene oxide with 2.5 to 3 mol of styrene and 1 mol of phenol, 4.0 parts of N,N'-ethylenebis(stearamide) 0.6 part of a biopolymer based on polysaccharide and 100 parts of water.
The dye is transferred by heating the pnnted transfer paper for 60 seconds at 230C.
A strong patterned print of good levelness, good fastness properties and with sharp contours is obtained.
Example 14: The procedure of Example 13 is repeated, except ~at ~he UV absorber is padded on to the fabric in arnounts of 1 to 4 % by weight before prin~ing. The paper is printed simultaneously with a print paste which contains no UV absorber. In the course of the transfer printing, the dye is transferred from the paper to the textile fabric and simultaneously fixed with the UV absorber.
A strong patterned print of good levelness, good fastness properties and with sharp contours is obtained on a white ground on the polyester fabric.
Claims (13)
1. A process for printing and for stabilising polyester fibre materials photochemically with disperse dyes and subsequently subjecting the materials to a heat treatment, which process comprises printing said materials with an aqueous print paste which, in addition to the disperse dye, contains a UV absorber.
2. A process according to claim 1, which comprises the use of a UV absorber which is resistant to sublimation at temperatures up to 165°C.
3. A process according to either claim 1 or claim 2, wherein the UV absorber is a hydroxyphenyl-s-triazine of formula (1) wherein R is C1-C5alkyl, C1-C5alkoxy, halogen, hydroxy, R1 and R2 are each independently of the other C1-C18alkyl, C1-C18alkyl which is substituted by hydroxy, C1-C5alkoxy, C1-C5alkylthio, amino or C1-C5mono- or C1-C5dialkylamino, phenyl or phenyl which is substituted by chloro, hydroxy, C1-C5alkyl and/or C1-C12alkoxy, or a radical of formula (OCH2-CH2)p-O-R3, n is 0, 1 or 2, p is 1 to 5 and R3 is hydrogen or C1-C5alkyl.
4. A process according to claim 3, wherein the UV absorber is an s-triazine of formula (2) wherein R is hydrogen or has the meaning given in formula(1), and R4 and R5 are each independently of the other unsubstituted phenyl or phenyl substituted by C1-C5alkyl and/or C1-C5-alkoxy, p is 1 to 5, and R6 is hydrogen or C1-C5alkyl.
5. A process according to claim 4, wherein the UV absorber is a compound of formula (3) wherein R7 is C1-C5alkyl or C1-C5alkoxy, R8 and R9 are each independently of the other unsubstituted phenyl or phenyl substituted by C1-C5alkyl and/or C1-C5alkoxy or a radical of the formula (OCH2-CH2)p1-O-R10, P1 is 1 to 3, and R10 is methyl or ethyl.
6. A process according to claim 5, wherein R7 is C1-C5alkoxy, and R8 and R9 are each independently of the other tolyl or xylyl.
7. A process according to claim 5, wherein R7 is C1-C5alkoxy and R8 and R9 are each phenyl.
8. A process according to claim 1 or 2, wherein the UV absorber is a benzotriazole of formula (4) wherein one of the substituents X1 and X2 is hydrogen and the other substituent of X1 and X2 is hydrogen or C1-C5alkyl, C1-C5alkoxy or halogen or the group in which R11 is hydrogen, C1-C10alkyl, C5-C8cycloalkyl, C7-C10aralkyl or C6-C10aryl, R12 is hydrogen, C1-C20alkyl, C2-C17alkenyl, C5-C8cycloalkyl, C7-C10aralkyl, C8-C10aralkenyl or C6-C10aryl, and m is 1 or 2, and if m = 1, R11 and R12, together with the ring linking group -?-CO-, may also form a mononuclear or polynuclear nitrogen-containing heterocycle and, in this case R11 is -CO- or unsubstituted methylene or C1-C5alkyl-substituted methylene, and R12 is C2-C5alkylene, C2-C5alkenylene, C6-C10arylene or vicinally bound di-, tetra- or hexahydro-C6-C10arylene, X3 is C1-C5alkyl, C1-C5alkoxy, halogen, C6-C10aryl, C7-C10aralkyl or C5-C8cycloalkyl, the ring A may be substituted in positions 1, 2 and 3 by C1-C5alkyl, C1-C5alkoxy, carboxy, C1-C5alkoxycarbonyl, H2NCO-, SO2-, C1-C5alkylsulfonyl or halogen.
9. A process according to claim 1 or 2, wherein the UV absorber is a benzophenone of formula (5) wherein R13 is hydrogen, hydroxy, C1-C14alkoxy or phenoxy, and C1-C14alkoxy can be substituted by a radical of formula and/or substituted by acyloxy, wherein R14 is hydrogen, halogen or C1-C5alkyl, R15 is hydrogen, hydroxy or C1-C5alkoxy, and R16 is hydrogen or hydroxy.
10. A process according 10 any one of claims 1 to 9, wherein the print paste contains 0.5 to 8 % of the UV absorber, based on the weight of the print paste.
11. Use of a UV absorber of formula (1), (4) or (5) as auxiliary for printing and for photochemically stabilising polyester fibre materials.
12. Use of a UV absorber of formula (1), (4) or (5) for enhancing the colour yield when printing polyester fibre materials.
13. The polyester fibre material treated according to any one of claims 1 to 12.14. Print paste containing 0.5 to 8 % of an UV absorber
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2086/91-5 | 1991-07-12 | ||
| CH208691 | 1991-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2073580A1 true CA2073580A1 (en) | 1993-01-13 |
Family
ID=4225570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002073580A Abandoned CA2073580A1 (en) | 1991-07-12 | 1992-07-10 | Process for printing and photochemically stabilising polyester fibre materials |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0523006B1 (en) |
| JP (1) | JPH05209374A (en) |
| AT (1) | ATE130883T1 (en) |
| BR (1) | BR9202579A (en) |
| CA (1) | CA2073580A1 (en) |
| DE (1) | DE59204472D1 (en) |
| DK (1) | DK0523006T3 (en) |
| ES (1) | ES2080473T3 (en) |
| GR (1) | GR3018250T3 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0657577A1 (en) * | 1993-12-06 | 1995-06-14 | Ciba-Geigy Ag | Process for photochemical and thermal stabilization of dyed and undyed or printed polyester fibrous materials |
| KR100414810B1 (en) * | 1995-03-17 | 2004-04-29 | 시바 스페셜티 케미칼스 홀딩 인크. | Liposome forming UV absorber |
| EP0864687A3 (en) * | 1997-03-11 | 1999-11-24 | Ciba SC Holding AG | Process for improving the photochemical stability of coloration and prints on polyester fibers |
| JP2009030214A (en) * | 2007-07-27 | 2009-02-12 | Senka Kk | Light fastness improver for fiber product, and method for improving light fastness |
| JP5072496B2 (en) * | 2007-09-11 | 2012-11-14 | 小松精練株式会社 | Method for decoloring flag for recycling and method for recycling flag |
| DE102007046745A1 (en) * | 2007-09-28 | 2009-04-02 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Disperse dye and / or UV absorber containing preparations |
| ES2463674T3 (en) | 2009-01-19 | 2014-05-28 | Basf Se | Organic black pigments and their preparation |
| DE102011082078A1 (en) * | 2011-09-02 | 2013-03-07 | Carl Stahl Gmbh & Co. Kg | Method for printing of belt strap for safety belt system of vehicle, involves applying ultraviolet-absorption agent on belt strap before printing in print ink, where print ink is applied over transfer paper on belt strap |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL126588C (en) * | 1961-06-16 | |||
| DE3417782A1 (en) * | 1983-05-23 | 1984-11-29 | Sandoz-Patent-GmbH, 7850 Lörrach | COLORING TOOLS |
| US4775386A (en) * | 1986-05-05 | 1988-10-04 | Ciba-Geigy Corporation | Process for photochemical stabilization of undyed and dyed polyamide fibre material and blends thereof with other fibres: copper complex and light stabilizer treatment |
| US4831068A (en) * | 1987-02-27 | 1989-05-16 | Ciba-Geigy Corporation | Process for improving the photochemical stability of dyeings on polyester fibre materials |
| DE58906867D1 (en) * | 1988-05-31 | 1994-03-17 | Ciba Geigy | Aqueous dispersion of 2- (2'-hydroxyphenyl) benzotriazoles. |
| ES2074688T5 (en) * | 1990-07-23 | 1998-11-01 | Ciba Geigy Ag | WATER DISPERSION OF LITTLE SOLUBLE UV ABSORBENTS. |
-
1992
- 1992-07-03 ES ES92810511T patent/ES2080473T3/en not_active Expired - Lifetime
- 1992-07-03 EP EP92810511A patent/EP0523006B1/en not_active Expired - Lifetime
- 1992-07-03 AT AT92810511T patent/ATE130883T1/en not_active IP Right Cessation
- 1992-07-03 DK DK92810511.3T patent/DK0523006T3/en active
- 1992-07-03 DE DE59204472T patent/DE59204472D1/en not_active Expired - Fee Related
- 1992-07-10 CA CA002073580A patent/CA2073580A1/en not_active Abandoned
- 1992-07-10 JP JP4206280A patent/JPH05209374A/en active Pending
- 1992-07-10 BR BR929202579A patent/BR9202579A/en not_active IP Right Cessation
-
1995
- 1995-11-30 GR GR950403168T patent/GR3018250T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0523006A1 (en) | 1993-01-13 |
| BR9202579A (en) | 1993-03-16 |
| DE59204472D1 (en) | 1996-01-11 |
| ES2080473T3 (en) | 1996-02-01 |
| ATE130883T1 (en) | 1995-12-15 |
| DK0523006T3 (en) | 1995-12-27 |
| JPH05209374A (en) | 1993-08-20 |
| GR3018250T3 (en) | 1996-02-29 |
| EP0523006B1 (en) | 1995-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5298030A (en) | Process for the photochemical and thermal stabilization of undyed and dyed or printed polyester fiber materials | |
| US4427413A (en) | Dye mixture, and its use in transfer printing | |
| KR950007820B1 (en) | Process for improving the photochemical stability of dyeing on polyester fiber materials | |
| AU653350B2 (en) | Aqueous dispersions of sparingly soluble UV absorbers | |
| CA2473180A1 (en) | Ink compositions containing lanthanide complexes | |
| CA2073580A1 (en) | Process for printing and photochemically stabilising polyester fibre materials | |
| EP0345219A1 (en) | Aqueous dispersions of 2-(2'-hydroxyphenyl) benzotriazoles | |
| US4093415A (en) | Transfer printing process for hydrophilic, synthetic fibre material or mixtures of hydrophilic and synthetic fibre material | |
| CA2137212A1 (en) | Process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materials | |
| US4264326A (en) | New disperse dyestuffs; their preparation and their applications to the coloration of synthetic materials | |
| EP0584044A1 (en) | Process for photochemical and thermal stabilization of undyert and dyert polyester fibrous materials | |
| US5984976A (en) | Process for improving the photochemical stability of dyeings and prints on polyester fibres | |
| US4306874A (en) | Process for printing synthetic, hydrophobic fiber material in accordance with the principle of transfer printing | |
| US4274831A (en) | Process for dyeing or printing synthetic fiber materials by means of disperse dyes, and colorant compositions utilizable for this purpose | |
| US4234481A (en) | Yellow pyrazolone ester dyes for heat transfer printing | |
| GB2041390A (en) | Alpha-hydrazone alpha-phenyl acetonitriles their preparation and their application as disperse dyestuffs for the colouration of artificial or synthetic materials | |
| KR100832223B1 (en) | Use of Pigments as Disperse Dyes | |
| US3409385A (en) | Anthraquinone dyed polypropylene fibers | |
| US4200570A (en) | 5-Halo-2-trifluoromethylphenylazo-pyrazolones | |
| CH470527A (en) | Process for dyeing and printing synthetic textile materials with anthraquinone dyes | |
| US4087241A (en) | Printing inks for transfer printing | |
| US3927964A (en) | 6-Anilino-1,4,5-trihydroxyanthraquinones | |
| EP0316731B1 (en) | Azo dyes from 2-hydrazinothiazole, their use in dyeing and printing fibre materials, and in sublimation transfer printing | |
| EP1366230A1 (en) | Use of pigment dyes for dispersion dyeing from aqueous media | |
| GB1569937A (en) | Dyes and their use in transfer printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |