CA2137212A1 - Process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materials - Google Patents
Process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materialsInfo
- Publication number
- CA2137212A1 CA2137212A1 CA 2137212 CA2137212A CA2137212A1 CA 2137212 A1 CA2137212 A1 CA 2137212A1 CA 2137212 CA2137212 CA 2137212 CA 2137212 A CA2137212 A CA 2137212A CA 2137212 A1 CA2137212 A1 CA 2137212A1
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- hydrogen
- formula
- c4alkyl
- phenyl
- compound
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Classifications
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- 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
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
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- Textile Engineering (AREA)
- Coloring (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Lightfast dyeings are obtained by the process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materials, which comprises treating said fibre material with at least one compound of formula (1), wherein R1 is the radical of formula (2), R2 and R'2 are each independently of the other hydrogen, C1-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and R5 is C1-C12alkyl, C1-C6monohaloalkyl, C1-C6dihaloalkyl, C1-C4alkenyl, C1-C4monohaloalkenyl, C5-C7cycloalkyl, phenyl; phenyl or phenyl-C1-C4alkyl, eachsubstituted by C1-C4alkyl, C1-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or
Description
. ..
Process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materials The present invention relates to a process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre m~teri:~l.c.
Undyed and dyed or printed polyester fibre materials are damaged by the action of light and, in particular, by the simultaneous action of heat. For use in the automotive field, the provision of an effective protection of undyed and dyed or printed fibre materials from UV radiation is indispensable.
Accordingly, the invention provides a process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre m~t~ , which comprises treating said materials with at least one compound of formula R'2 /~N ~R1 (1), wherein Rl is the radical of formula 1l -CH2-N-C-Rs (2), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8aLkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and R5 is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6dihaloalkyl, Cl-C4alkenyl, Cl-C4monohaloalkenyl, C5-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula ~1372~2 ---N (CH2) (3a),--N~/ (3b)or--N~3R7 (3c), wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen.
In the formulae shown above the substituents have the following meanings:
Halogen is typically fluoro, bromo and, preferably, chloro.
Cl-Cl2Alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl or n-decyl.
Cs-C7Cycloalkyl is typically cyclopentyl, cyclohexyl or cycloheptyl.
(Cl-C8Alkyl)phenyl is typically methylphenyl, ethylphenyl, tert-butylphenyl or di-tert-butylphenyl .
C7-CgPhenylalkyl is typically benzyl or phenethyl.
Cl-C4Alkoxy is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy.
Cl-C4Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
Cl-C6Monohaloalkyl is typically chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloro-n-propyl or 4-chloro-n-butyl.
Cl-C6Dihaloalkyl is typically 1,2-dichloroethyl, 1,2-dibromoethyl or 2,3-dichlc,loplopyl.
C2-C4Alkenyl is typically vinyl, 2-propenyl or 2-butenyl.
C2-C4Monohaloalkenyl is typically l-chloroethen- l-yl, or l-bromoethen- l-yl.
2~ 2 Phenyl-C1-C4alkyl is typically benzyl or phenethyl.
~;felled compounds used in the process of this invention are those of formula ~N
wherein Rl, R2 and R3 are as deffned in formula (1). It is particularly pl~,f~l~,d to use those compounds of formula (4), wherein Rl is the radical of formula 1l -CH2-N-C-Rs (2), R2 is hydrogen, C1-Cl2alkyl, Cs-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and Rs is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6 (lih~lo~lkyl, Cl-C4alkenyl, Cl-C4m-~noh~loalkenyl, Cs-C7cycloalkyl, unsubstituted phenyl or phenyl which is substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-C0- radical, form a radical of formula --N (CH2) (3a),--N~ (3b) or--N~ R7 (3c), wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, C1-C4alkoxy or halogen.
A particularly preferred process is that comprising the use of at least one compound of formula (1) or (4), wherein R1 is a radical of formula (2), R2 is hydrogen, Cl-C4alkyl, C5-C7cycloalkyl, (Cl-C4alkyl)phenyl, phenyl, benzyl or phenethyl, ;~ 372i2 R'2 is hydrogen or Cl-C4alkyl, R3 is hydrogen, chloro or bromo, R4 is hydrogen, and Rs is Cl-C6alkyl, Cl-C4chloroalkyl, Cl-C4dichloroalkyl, Cl-C4dibromoalkyl, Cl-C4alkenyl, Cl-C4chloroalkenyl, Cl-C4bromoalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or benzyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy, chloro or bromo, or R4 and Rs, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or (3c), wherein n is 2, 3 or 4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl or halogen.
If the compound of formula (4) is used, then R'2 is hydrogen.
A very particularly ~lefe,l~d process comprises using at least one compound of formula ~N ~
wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R8 is methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl, n-butyl, phenyl, chlorophenyl, dichlorophenyl, 1,2-dichloroethyl, 1,2-dibromoethyl, cyclohexyl, l-chlorovinyl or l-bromovinyl.
A further very particularly preferred process comprises using at least one compound of formula ~--N`N ~ (6), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, Z137i~2 R3 is hydrogen or chloro, and Rg is a radical of formula (3a), (3b) or (3c), wherein n iS 3, R6 is hydrogen or methyl, and R7 is hydrogen.
An important process of this invention comprises using at least one compound of formula R~ R2 )~--N~N ~ (7), R3 OH R~2 wherein Rl, R2, R'2 and R3 are as defined in formula (1) and, in particular, wherein Rl, R2, R'2 and R3 have the meanings cited above for a particularly pl~felled process.
A further particularly important process compn~es using a mixture of at least one compound of formula (1) and a compound of formula )~N ~R 2 (8), wherein R2, R'2 and R3 are as defined for formula (1). Especially suitable n~ ult;s are those wherein at least one compound of formula (1) is used together with a compound of formula (8), wherein Rl, R2, R'2 and R3 have the meanings cited above as prefell~d and as particularly plerell~d.
A very particularly important process comprises using a mixture of two compounds of formula (1).
In the process of this invention there are used not only individual compounds of formula (1), but also mixtures of compounds of formula (1), and Ini~c~ul.,s of compounds of formula (1) and at least one compound of formula (8). The mixtures usually comprise two or also three compounds of formula (1). It is preferred to use two compounds of formula (1) in the novel process.
Some of the compounds of formula (1) are novel. The novel compounds of formula (la) ;~37~2 are also an object of the present invention.
The novel compounds have the formula /~CN ~ (la), wherein Rl is the radical of formula -CH2-N-C-R5 (2a), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2aLkyl, C5-C7cycloaLkyl, (Cl-C8aLkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4aLkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and Rs is Cl-Cl2alkyl, C2-C6monohaloalkyl, Cl-C6dihaloalkyl, Cl-C4aLkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, each substituted by Cl-C4alkyl, Cl-C4aLkoxy or halogen, or R4 and Rs, together with the linking -N-CO- radical, form a radical of formula N)~/ 2 (3a~)--N~3/ (3b') or--N~ R7 (3c'), wherein n is 1, 2, 3 or 4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen, or wherein Rl is the radical of formula -CH2-N(R4)-CO-CH2-Cl, R2 is hydrogen, C2-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-CgphenylaLkyl or Cl-C4alkoxy, R3 is hydrogen or halogen, and R4 is hydrogen or Cl-C4alkyl.
F~lt;rellt;d compounds are those of forrnula ~ 2~37Z12 )~ N ~ (4a), wherein Rl, R2 and R3 are as defined in formula (la) and, in particular, wherein Rl is the radical of formula -CH2-N-C-Rs (2a), R2 is hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and Rs is Cl-Cl2aLkyl, Cl-C6monohaloalkyl, Cl-C6~ih~lo~lkyl, Cl-C4alkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, unsubstituted phenyl or phenyl which is substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-C0- radical, form a radical of formula --N~ ei (3a ), N~/ (3b ) or N~3 R7 (3C'), wherem nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen.
Particularly preferred compounds are those of formulae (la) and (4a), wherein Rl is the radical of formula (2a), R2 is hydrogen, Cl-C4alkyl, Cs-C7cycloalkyl, (Cl-C4alkyl)phenyl, phenyl, benzyl or phenethyl, R'2 is hydrogen or Cl-C4alkyl, R3 is hydrogen, chloro or bromo, R4 is hydrogen, and Rs is Cl-C6alkyl, C2-C4chloroalkyl, Cl-C4dichloroalkyl, C2-C4dibromoalkyl, Cl-C4alkenyl, Cl-C4chloroalkenyl, Cl-C4bromoalkenyl, Cs-C7cycloalkyl, phenyl; phenyl 2~37Z12 or benzyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy, chloro or bromo, or R4 and R5, together with the linking -N-CO- radical, forrn a radical of formula (3a'), (3b') or (3c'), wherein n is 2, 3 or 4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl or halogen.
Very particularly plefell.,d compounds are those of formula ~--N`N ~ (Sa), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R8 is methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl, n-butyl, phenyl, chlorophenyl, dichlorophenyl, 1,2-dichloroethyl, 1,2-dibromoethyl, cyclohexyl, 1-chlorovinyl or 1-bromovinyl.
Very particularly ~ ,d compounds are also those of formula ~--N~ ~ (6a), R3 OH CH2- Rg wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and Rg is a radical of for nula (3a'), (3b') or (3c'), wherein n is 3, R6 is hydrogen or methyl, and R7 is hydrogen.
Further important compounds are those of formula 2~37i~12 )~ N ~ (7a), R3 OH R'2 wherein Rl, R2, R'2 and R3 are as defined in formula (la) and, in particular, those wherein Rl, R2, R'2 and R3 have the meanings cited above for the particularly plt;felledcompounds.
The compounds of forrnulae (1) and (la) are prepared by reacting a compound of formula ~[~ N ~ R'2 (8), wherein R2, R'2 and R3 are as defined for each of formulae (1) and (la), with a compound which introduces the radical of formula -CH2-N-C-Rs (2) and (2a) wherein R4 and R5 are as defined for each of formulae (2) and (2a).
The reaction is carried out in the L~mpel~ture range from 0 to 100C, typically by homogenising the compounds of formula (7) and the compound which introduces the radical of formula (2) and by adding the l..i~ ;, with stirring, to conce~ led sulfuric acid. The reaction mass is then poured on ice/water and the product is isolated in per se known manner.
Accordingly, a further object of the present invention is a process for the preparation of compounds of formula (la).
Compounds of formula (8) and (8a) and the compounds which introduce the radical of formula (2) and (2a) are known and may be prepared by processes analogous to known ones.
Illustrative examples of compounds of formula (8) and (8a) are:
.... 2137212 [~ N ~ Cl~[ N
Typical examples of compounds which introduce the radical of formulae (2) and (2a) are the following:
N-hydroxymethylben7~mide, N-hydroxymethylacet~micle, N-hydroxymethyl-4-chloro-ben7~mi~e, N-hydroxymethyl-2,4-dichloroben7~mille, N-hydroxymethylbutyramide, N-hydroxymethyl-2,3-dichlol o~l opionamide, N-hydroxymethyl-2,3-dibromo-propionamide.
The invention further relates to a process for the photochemical and thermal stabilisation of undyed polyester fibre materials, which comprises treating said fibre material with a dye liquor containing, in addition to a disperse dye, a compound of formula )~N ~R~
wherein Rl is the radical of formula -CH2-N-C-Rs (2), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4-Alkyl, and Rs is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6dihaloalkyl, C1-C4alkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-CO- radical, form a radical of formula --N (CH2) (3a),--N~/ (3b) or--N~3 R7 (3c), 1~ b 2 1 3 72 1 2 wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen.
The invention further relates to mixtures cont~ining at least one compound, in particular 2 or 3 and, preferably, 2 compounds of formula --N~N ~R'2 (1), N >~R, wherein Rl is the radical of formula -CH2-N-C-R5 (2), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and Rs is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6~1ih~lo~lkyl, Cl-C4alkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, eachsubstituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-C0- radical, form a radical of formula )~ 2 (3a) N~ (3b) or--N~3 R7 (3c), wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen and, in particular, mixtures containing, in addition to at least one compound of formula ( 1), a compound of formula /~ N ~ R'2 (8), wherein R2, R'2 and R3 are as defined above.
The identical preferences cited above in connection with the compounds of formula (1) apply to the mixtures of the compounds of formula (1) as well as to the mixtures of at least one compound of formula (1) with a compound of formula (8).
The UV absorbers of this invention are used in an amount of 0.01 to 5 % by weight, preferably 0.1 to 3% by weight and, most preferably, 0.25 to 2% by weight, based on the weight of the fibre material.
In the mixtures of this invention, the ratio of the compounds of formula (1) or of at least one compound of formula (1) and one compound of formula (8) may vary over a widerange: a preferred ratio of two compounds of formula (1) or of one compound of formula (1) and one compound of formula (8) is from 1:1 to 10:1; and the ratio of two compounds of formula (1) and one compound of formula (8) is preferably from 1:10:1, 10:1:10 to 10:10:1.
The UV absorbers of this invention are almost insoluble in water and are therefore applied in dispersed form. To this end they are milled with an applop,iate dispersant, conveniently using quartz balls and an impeller, to a particle size of 1-2 ~lm.
Suitable dispersants for the UV absorbers of formula (1) are:
- acid esters or their salts of alkylene oxide ~(ld~lcts, typically acid esters or their salts of a polyadduct of 4 to 40 mol of ethylene oxide with 1 mol of a phenol, or phosphated polyadducts of 6 to 30 mol of ethylene oxide with 1 mol of 4-nonylphenol, 1 mol of dinonylphenol or, preferably, with 1 mol of compounds which are prepared by addition of 1 to 3 mol of styrenes to 1 mol of phenol, - polystyrene sulfonates, - fatty acid taurides, - alkylated diphenyl oxide mono- or disulfonates, - sulfonates of polycarboxylates, ~21 3721 2 - the polyadducts of 1 to 60 mol, preferably 2 to 30 mol, of ethylene oxide and/or propylene oxide with fatty amines, fatty amides, fatty acids or fatty alcohols, each cont~ining 8 to 22 carbon atoms, or with trivalent or hexavalent aLkanols of 3 to 6 carbon atoms, which polyadducts are converted into an acid ester with an organicdicarboxylic acid or with an inorganic polybasic acid, - ligninsulfonates, and, most preferably, - fonn~ldehyde conden~tes such as condensates of lignin~l11fonates and/or phenol and fnrm~l-lehyde, condens~tes of formaldehyde with aromatic sulfonic acids, typically condensates of ditolyl ether sulfonates and formaldehyde, conflens~t~-s of naphthalenesulfonic acid and/or naphthol- or naphthyl~minesulfonic acids with formaldehyde, conden~tes of phenolsulfonic acids and/or sulfonated dihydroxydi-phenylsulfone and phenols or cresols with formaldehyde and/or urea, as well as condensates of diphenyl oxide-disulfonic acid derivatives with formaldehyde.
Suitable dyes are disperse dyes which are only sparingly soluble in water. They are therefore substantially present in the dye liquor in the form of a fine dispersion. They may belong to different dye classes, including the acridone, azo, anthraquinone, coumarin, methine, perinone, naphthoquinone-imine, quinophthalone, styryl or nitro dyes. Mixtures of disperse dyes may also be used in the practice of this invention.
Polyester fibre material which can be dyed or printed and treated with the citedUV absorbers will be understood as including cellulose ester fibres such as cellulose secondary acetate and cellulose triacetate fibres and, preferably, linear polyester fibres which may also be acid-modified, and which are obtained by the conden~tion of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis(hydroxymethyl)cyclohexane, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol, or the incorporation of sulfoisophthalic acid. The linear polyester fibre material hitherto used almost exclusively in the textile industry consists of terephthalic acid and ethylene glycol.
The fibre materials may also be used as blends with each other or with other fibres, typically blends of polyacrylonitrile/polyester, polyamide/polyester, polyester/cotton, polyester/viscose and polyester/wool, and they can be dyed or also printed batchwise or continuously by known methods.
The textile material can be in different forms of presentation, preferably as piece goods 21372~2 such as knitgoods or wovens or also as yarn on cheeses, warp beams and the like.
Dyeing is carried out from an aqueous liquor by a continuous or batch process. In batchwise dyeing, the liquor ratio may be chosen over a wide range, typically from 1:4 to 1:100, preferably from 1:6 to 1:50. The dyeing teml!eralure is at least 50C and is normally not higher than 140C. The plefelled temperature range is from 80 to 135C.
In continuous dyeing methods, the dye liquors, which may contain further auxiliaries in addition to the dyes, are applied to the piece goods by padding or slop-padding and developed by thermofixation or HT ste~ming processes.
Linear polyester fibres and cellulose fibres are preferably dyed by the high temperature process in closed and pressure-resistant apparatus in the temperature range >100C, preferably in the range from 110 to 135C, and at normal or elevated pressure. Suitable closed apparatus includes typically circulation dyeing m~hines such as cheese or beam dyeing machines, winch becks, jet or drum dyeing machines, muff dyeing machines,paddles or jiggers.
For continuous dyeing, padders or lick rollers are used and development is carried out with hot air in stenter frames or in HT steamers.
Cellulose secondary acetate is preferably dyed in the temperature range from 80-85C.
When using the novel UV absorbers for dye application, the procedure is such that the fibre material is first treated with these compounds and then dyeing is carried out or, preferably, the fibre material is treated simultaneously in the dyebath with theUV absorber and the dye. The application of the UV absorber can, however, also be made subsequently to the ready prepared dyeing by padding and thermofixation, conveniently at 190-230C over a period of 30 seconds to 5 minutes.
The dye liquors may also contain further ingredients such as dyeing assistants, dispersants, diffusion accelerators, wool protectives, and wetting agents as well as antifoams.
The dyebaths may also contain mineral acids, typically sulfuric acid or phosphoric acid, or conveniently organic acids, typically aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and/or salts such as ammonium acetate, ammonium ;~3!37Z~2 sulfate or sodium acetate. The acids are used in particular to adjust the pH of the liquors used in the practice of this invention to 4-5.
Preferably the fibre material is first run over S minutes at 40-80C in the bath which contains the dye, the UV absorber and any further auxiliaries and which has been adjusted to pH 4.5-5.5. Then the temperature is raised to 125-130C over 10 to 20 minutes and further treatment is carried out for 15 to 90 minutes, preferably for 30 minutes, at this len,pc;l~ture.
The dyeings are finished by cooling the dye liquor to 50-80C, washing off the dyeings with water and, if nçcess~ry, reduction clearing them in conventional manner in ~lk~line medium. The dyeings are then again washed off and dried.
For producing prints, the novel UV absorbers are mixed in the form of aqueous dispersions with the print pastes. The print paste then contains the UV absorber in an amount of 0.5 to 5 %, preferably 1 to 2 %, based on the weight of the fibre material to be printed.
The amount of dye added to the print pastes will depend on the desired shade. Normally amounts of 0.01 to 15 % by weight, preferably of 0.02 to 10 % by weight, based on the textile material to be used, have been found useful.
In addition to containing the dyes and the aqueous dispersion of the 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 admixture with modified cellulose, preferably with 20 to 25 % by weight of carboxymethyl cellulose. The print pastes may additionally contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, sequestrants, emulsifiers, water-insoluble solvents, oxidising agents or dearators.
Particularly suitable preservatives are formaldehyde donors such as parafonn~ldehyde or trioxane, preferably c. 30 to 40 % by weight aqueous formaldehyde solutions. Suitable sequestrants are typically sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, preferably sodium polymethaphosphate, more particularly sodium hexamethaphosphate.
Emulsifiers are preferably polyadducts of an alkylene oxide and a fatty alcohol, more particularly a polyadduct of oleyl alcohol and ethylene oxide. Water-insoluble solvents are ;~3L372,~
preferably high-boiling saturated hydrocarbons, more particularly paraffins having a boiling range from about 160 to 210C (white spirits). Oxidising agents are typically aromatic nitro compounds, preferably an aromatic mono- or dinitrocarboxylic acid or mono- or dinitrosulfonic acid which may be in the form of an alkylene oxide polyadduct, preferably a nitrobenzenesulfonic acid. Deaerators are suitably high-boiling solvents, preferably terpentine oils, higher alcohols, in particular C8-Cl0alcohols, terpene alcohols or deaerators based on mineral and/or silicone oils, preferably commercial formulations comprising about 15-25 % by weight of a Illi~Ule of mineral and silicone oils and about 75-85 % by weight of a C8alcohol such as 2-ethyl-n-hexanol.
For printing the fibre materials, the print paste is applied direct to the whole or to a part of the surface, conveniently using printing machines of conventional construction, typically rotogravure, rotary screen printing and surface screen printing m~chines.
The fibre material is dried after printing in the tempeldtule range up to 150C, preferably in the range from 80 to 120C.
The subsequent fixation of the fibre material is usually carried out by a heat treatment, preferably in the temperature range from 100 to 220. The heat treatment is norm~lly carried out with superheated steam under atmospheric pressure.
Depending on the temperature, fixation is carried out for 20 seconds to 10 minutes, preferably for 4 to 8 minutes.
The prints are also finished in conventional manner by washing off with water, followed by an optional reductive afterclear in alkaline medium, conveniently with sodiumdithionite. In this last mentioned case, the prints are again washed off, hydroextracted and dried.
For transfer printing, the printing paste is coated on paper and subsequently transferred from the paper to the fibre material. Transfer printing on the calendering machine is preferably carried out at 210-240C over 20 to 60 seconds.
The process of this invention makes it possible to obtain polyester dyeings and prints of excellent fastness to light and sublimation and which are suitable for use in automobile upholstery as well as in canvas, nets and belts, but also for so-called out-door articles such ~:~37~i;2 as sun shades, sun blinds and awnings. The process of this invention requires no specific pretreatment or aftertre~tment of the fibre material. In addition, a reduction of the diffuse tr~n~mi~sion of UV radiation through textiles made from polyester fibres as well as from polyester fibre blends is achieved with the polyester fibre materials which have been treated with the compounds of formula (1).
In the following working and application Examples percentages are by weight. Theamounts of dye and UV absorbers are based on pure substance.
Preparation of the UV absorbers Exmample 1: 135 g of the compound of formula ~N~ ~ (100) OH
and 132 g of N-hydroxymethylben7~mide are homogenised and then added, with stirring, over 90 minutes at 0-5C to 660 ml of sulfuric acid (95-97%). The reaction is allowed to go to completion for 2 hours at 0-5C. The viscous, yellow solution is then poured over 20 minutes into 3000 g of a mixture of ice/water of 0-5C. The resultant pale yellow suspension is stirred for 30 minutes and filtered. Subsequently, the filter product is washed with water until neutral and then dried, giving 206 g (96% of theory) of the compound of formula HO~CH2NHCO~ (101).
The procedure of Example 1 is repeated, but using as benzotriazole a compound offormula /~N ~ , wherein R2 and R3 are as defined in Table 1, and replacing N-hydroxymethylben7~mide by an equivalent amount of a compound of formula 2~372~
Ho-cH2-R , wherein R is as defined in Table 1, to give compounds of formula ~ N~ ~ , wherein R, Rl and R3 are as defined in Table 1.
R3 OH Rl ~3~2 ~....
Table 1 Example R3 R2 R *m.p.C
Process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materials The present invention relates to a process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre m~teri:~l.c.
Undyed and dyed or printed polyester fibre materials are damaged by the action of light and, in particular, by the simultaneous action of heat. For use in the automotive field, the provision of an effective protection of undyed and dyed or printed fibre materials from UV radiation is indispensable.
Accordingly, the invention provides a process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre m~t~ , which comprises treating said materials with at least one compound of formula R'2 /~N ~R1 (1), wherein Rl is the radical of formula 1l -CH2-N-C-Rs (2), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8aLkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and R5 is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6dihaloalkyl, Cl-C4alkenyl, Cl-C4monohaloalkenyl, C5-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula ~1372~2 ---N (CH2) (3a),--N~/ (3b)or--N~3R7 (3c), wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen.
In the formulae shown above the substituents have the following meanings:
Halogen is typically fluoro, bromo and, preferably, chloro.
Cl-Cl2Alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl or n-decyl.
Cs-C7Cycloalkyl is typically cyclopentyl, cyclohexyl or cycloheptyl.
(Cl-C8Alkyl)phenyl is typically methylphenyl, ethylphenyl, tert-butylphenyl or di-tert-butylphenyl .
C7-CgPhenylalkyl is typically benzyl or phenethyl.
Cl-C4Alkoxy is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy.
Cl-C4Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
Cl-C6Monohaloalkyl is typically chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloro-n-propyl or 4-chloro-n-butyl.
Cl-C6Dihaloalkyl is typically 1,2-dichloroethyl, 1,2-dibromoethyl or 2,3-dichlc,loplopyl.
C2-C4Alkenyl is typically vinyl, 2-propenyl or 2-butenyl.
C2-C4Monohaloalkenyl is typically l-chloroethen- l-yl, or l-bromoethen- l-yl.
2~ 2 Phenyl-C1-C4alkyl is typically benzyl or phenethyl.
~;felled compounds used in the process of this invention are those of formula ~N
wherein Rl, R2 and R3 are as deffned in formula (1). It is particularly pl~,f~l~,d to use those compounds of formula (4), wherein Rl is the radical of formula 1l -CH2-N-C-Rs (2), R2 is hydrogen, C1-Cl2alkyl, Cs-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and Rs is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6 (lih~lo~lkyl, Cl-C4alkenyl, Cl-C4m-~noh~loalkenyl, Cs-C7cycloalkyl, unsubstituted phenyl or phenyl which is substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-C0- radical, form a radical of formula --N (CH2) (3a),--N~ (3b) or--N~ R7 (3c), wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, C1-C4alkoxy or halogen.
A particularly preferred process is that comprising the use of at least one compound of formula (1) or (4), wherein R1 is a radical of formula (2), R2 is hydrogen, Cl-C4alkyl, C5-C7cycloalkyl, (Cl-C4alkyl)phenyl, phenyl, benzyl or phenethyl, ;~ 372i2 R'2 is hydrogen or Cl-C4alkyl, R3 is hydrogen, chloro or bromo, R4 is hydrogen, and Rs is Cl-C6alkyl, Cl-C4chloroalkyl, Cl-C4dichloroalkyl, Cl-C4dibromoalkyl, Cl-C4alkenyl, Cl-C4chloroalkenyl, Cl-C4bromoalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or benzyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy, chloro or bromo, or R4 and Rs, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or (3c), wherein n is 2, 3 or 4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl or halogen.
If the compound of formula (4) is used, then R'2 is hydrogen.
A very particularly ~lefe,l~d process comprises using at least one compound of formula ~N ~
wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R8 is methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl, n-butyl, phenyl, chlorophenyl, dichlorophenyl, 1,2-dichloroethyl, 1,2-dibromoethyl, cyclohexyl, l-chlorovinyl or l-bromovinyl.
A further very particularly preferred process comprises using at least one compound of formula ~--N`N ~ (6), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, Z137i~2 R3 is hydrogen or chloro, and Rg is a radical of formula (3a), (3b) or (3c), wherein n iS 3, R6 is hydrogen or methyl, and R7 is hydrogen.
An important process of this invention comprises using at least one compound of formula R~ R2 )~--N~N ~ (7), R3 OH R~2 wherein Rl, R2, R'2 and R3 are as defined in formula (1) and, in particular, wherein Rl, R2, R'2 and R3 have the meanings cited above for a particularly pl~felled process.
A further particularly important process compn~es using a mixture of at least one compound of formula (1) and a compound of formula )~N ~R 2 (8), wherein R2, R'2 and R3 are as defined for formula (1). Especially suitable n~ ult;s are those wherein at least one compound of formula (1) is used together with a compound of formula (8), wherein Rl, R2, R'2 and R3 have the meanings cited above as prefell~d and as particularly plerell~d.
A very particularly important process comprises using a mixture of two compounds of formula (1).
In the process of this invention there are used not only individual compounds of formula (1), but also mixtures of compounds of formula (1), and Ini~c~ul.,s of compounds of formula (1) and at least one compound of formula (8). The mixtures usually comprise two or also three compounds of formula (1). It is preferred to use two compounds of formula (1) in the novel process.
Some of the compounds of formula (1) are novel. The novel compounds of formula (la) ;~37~2 are also an object of the present invention.
The novel compounds have the formula /~CN ~ (la), wherein Rl is the radical of formula -CH2-N-C-R5 (2a), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2aLkyl, C5-C7cycloaLkyl, (Cl-C8aLkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4aLkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and Rs is Cl-Cl2alkyl, C2-C6monohaloalkyl, Cl-C6dihaloalkyl, Cl-C4aLkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, each substituted by Cl-C4alkyl, Cl-C4aLkoxy or halogen, or R4 and Rs, together with the linking -N-CO- radical, form a radical of formula N)~/ 2 (3a~)--N~3/ (3b') or--N~ R7 (3c'), wherein n is 1, 2, 3 or 4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen, or wherein Rl is the radical of formula -CH2-N(R4)-CO-CH2-Cl, R2 is hydrogen, C2-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-CgphenylaLkyl or Cl-C4alkoxy, R3 is hydrogen or halogen, and R4 is hydrogen or Cl-C4alkyl.
F~lt;rellt;d compounds are those of forrnula ~ 2~37Z12 )~ N ~ (4a), wherein Rl, R2 and R3 are as defined in formula (la) and, in particular, wherein Rl is the radical of formula -CH2-N-C-Rs (2a), R2 is hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and Rs is Cl-Cl2aLkyl, Cl-C6monohaloalkyl, Cl-C6~ih~lo~lkyl, Cl-C4alkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, unsubstituted phenyl or phenyl which is substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-C0- radical, form a radical of formula --N~ ei (3a ), N~/ (3b ) or N~3 R7 (3C'), wherem nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen.
Particularly preferred compounds are those of formulae (la) and (4a), wherein Rl is the radical of formula (2a), R2 is hydrogen, Cl-C4alkyl, Cs-C7cycloalkyl, (Cl-C4alkyl)phenyl, phenyl, benzyl or phenethyl, R'2 is hydrogen or Cl-C4alkyl, R3 is hydrogen, chloro or bromo, R4 is hydrogen, and Rs is Cl-C6alkyl, C2-C4chloroalkyl, Cl-C4dichloroalkyl, C2-C4dibromoalkyl, Cl-C4alkenyl, Cl-C4chloroalkenyl, Cl-C4bromoalkenyl, Cs-C7cycloalkyl, phenyl; phenyl 2~37Z12 or benzyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy, chloro or bromo, or R4 and R5, together with the linking -N-CO- radical, forrn a radical of formula (3a'), (3b') or (3c'), wherein n is 2, 3 or 4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl or halogen.
Very particularly plefell.,d compounds are those of formula ~--N`N ~ (Sa), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R8 is methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl, n-butyl, phenyl, chlorophenyl, dichlorophenyl, 1,2-dichloroethyl, 1,2-dibromoethyl, cyclohexyl, 1-chlorovinyl or 1-bromovinyl.
Very particularly ~ ,d compounds are also those of formula ~--N~ ~ (6a), R3 OH CH2- Rg wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and Rg is a radical of for nula (3a'), (3b') or (3c'), wherein n is 3, R6 is hydrogen or methyl, and R7 is hydrogen.
Further important compounds are those of formula 2~37i~12 )~ N ~ (7a), R3 OH R'2 wherein Rl, R2, R'2 and R3 are as defined in formula (la) and, in particular, those wherein Rl, R2, R'2 and R3 have the meanings cited above for the particularly plt;felledcompounds.
The compounds of forrnulae (1) and (la) are prepared by reacting a compound of formula ~[~ N ~ R'2 (8), wherein R2, R'2 and R3 are as defined for each of formulae (1) and (la), with a compound which introduces the radical of formula -CH2-N-C-Rs (2) and (2a) wherein R4 and R5 are as defined for each of formulae (2) and (2a).
The reaction is carried out in the L~mpel~ture range from 0 to 100C, typically by homogenising the compounds of formula (7) and the compound which introduces the radical of formula (2) and by adding the l..i~ ;, with stirring, to conce~ led sulfuric acid. The reaction mass is then poured on ice/water and the product is isolated in per se known manner.
Accordingly, a further object of the present invention is a process for the preparation of compounds of formula (la).
Compounds of formula (8) and (8a) and the compounds which introduce the radical of formula (2) and (2a) are known and may be prepared by processes analogous to known ones.
Illustrative examples of compounds of formula (8) and (8a) are:
.... 2137212 [~ N ~ Cl~[ N
Typical examples of compounds which introduce the radical of formulae (2) and (2a) are the following:
N-hydroxymethylben7~mide, N-hydroxymethylacet~micle, N-hydroxymethyl-4-chloro-ben7~mi~e, N-hydroxymethyl-2,4-dichloroben7~mille, N-hydroxymethylbutyramide, N-hydroxymethyl-2,3-dichlol o~l opionamide, N-hydroxymethyl-2,3-dibromo-propionamide.
The invention further relates to a process for the photochemical and thermal stabilisation of undyed polyester fibre materials, which comprises treating said fibre material with a dye liquor containing, in addition to a disperse dye, a compound of formula )~N ~R~
wherein Rl is the radical of formula -CH2-N-C-Rs (2), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4-Alkyl, and Rs is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6dihaloalkyl, C1-C4alkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, each substituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-CO- radical, form a radical of formula --N (CH2) (3a),--N~/ (3b) or--N~3 R7 (3c), 1~ b 2 1 3 72 1 2 wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen.
The invention further relates to mixtures cont~ining at least one compound, in particular 2 or 3 and, preferably, 2 compounds of formula --N~N ~R'2 (1), N >~R, wherein Rl is the radical of formula -CH2-N-C-R5 (2), R2 and R'2 are each independently of the other hydrogen, Cl-Cl2alkyl, Cs-C7cycloalkyl, (Cl-C8alkyl)phenyl, phenyl, C7-Cgphenylalkyl or Cl-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or Cl-C4alkyl, and Rs is Cl-Cl2alkyl, Cl-C6monohaloalkyl, Cl-C6~1ih~lo~lkyl, Cl-C4alkenyl, Cl-C4monohaloalkenyl, Cs-C7cycloalkyl, phenyl; phenyl or phenyl-Cl-C4alkyl, eachsubstituted by Cl-C4alkyl, Cl-C4alkoxy or halogen, or R4 and Rs, together with the linking -N-C0- radical, form a radical of formula )~ 2 (3a) N~ (3b) or--N~3 R7 (3c), wherein nis 1,2,30r4, R6 is hydrogen or Cl-C4alkyl, and R7 is hydrogen, Cl-C4alkyl, Cl-C4alkoxy or halogen and, in particular, mixtures containing, in addition to at least one compound of formula ( 1), a compound of formula /~ N ~ R'2 (8), wherein R2, R'2 and R3 are as defined above.
The identical preferences cited above in connection with the compounds of formula (1) apply to the mixtures of the compounds of formula (1) as well as to the mixtures of at least one compound of formula (1) with a compound of formula (8).
The UV absorbers of this invention are used in an amount of 0.01 to 5 % by weight, preferably 0.1 to 3% by weight and, most preferably, 0.25 to 2% by weight, based on the weight of the fibre material.
In the mixtures of this invention, the ratio of the compounds of formula (1) or of at least one compound of formula (1) and one compound of formula (8) may vary over a widerange: a preferred ratio of two compounds of formula (1) or of one compound of formula (1) and one compound of formula (8) is from 1:1 to 10:1; and the ratio of two compounds of formula (1) and one compound of formula (8) is preferably from 1:10:1, 10:1:10 to 10:10:1.
The UV absorbers of this invention are almost insoluble in water and are therefore applied in dispersed form. To this end they are milled with an applop,iate dispersant, conveniently using quartz balls and an impeller, to a particle size of 1-2 ~lm.
Suitable dispersants for the UV absorbers of formula (1) are:
- acid esters or their salts of alkylene oxide ~(ld~lcts, typically acid esters or their salts of a polyadduct of 4 to 40 mol of ethylene oxide with 1 mol of a phenol, or phosphated polyadducts of 6 to 30 mol of ethylene oxide with 1 mol of 4-nonylphenol, 1 mol of dinonylphenol or, preferably, with 1 mol of compounds which are prepared by addition of 1 to 3 mol of styrenes to 1 mol of phenol, - polystyrene sulfonates, - fatty acid taurides, - alkylated diphenyl oxide mono- or disulfonates, - sulfonates of polycarboxylates, ~21 3721 2 - the polyadducts of 1 to 60 mol, preferably 2 to 30 mol, of ethylene oxide and/or propylene oxide with fatty amines, fatty amides, fatty acids or fatty alcohols, each cont~ining 8 to 22 carbon atoms, or with trivalent or hexavalent aLkanols of 3 to 6 carbon atoms, which polyadducts are converted into an acid ester with an organicdicarboxylic acid or with an inorganic polybasic acid, - ligninsulfonates, and, most preferably, - fonn~ldehyde conden~tes such as condensates of lignin~l11fonates and/or phenol and fnrm~l-lehyde, condens~tes of formaldehyde with aromatic sulfonic acids, typically condensates of ditolyl ether sulfonates and formaldehyde, conflens~t~-s of naphthalenesulfonic acid and/or naphthol- or naphthyl~minesulfonic acids with formaldehyde, conden~tes of phenolsulfonic acids and/or sulfonated dihydroxydi-phenylsulfone and phenols or cresols with formaldehyde and/or urea, as well as condensates of diphenyl oxide-disulfonic acid derivatives with formaldehyde.
Suitable dyes are disperse dyes which are only sparingly soluble in water. They are therefore substantially present in the dye liquor in the form of a fine dispersion. They may belong to different dye classes, including the acridone, azo, anthraquinone, coumarin, methine, perinone, naphthoquinone-imine, quinophthalone, styryl or nitro dyes. Mixtures of disperse dyes may also be used in the practice of this invention.
Polyester fibre material which can be dyed or printed and treated with the citedUV absorbers will be understood as including cellulose ester fibres such as cellulose secondary acetate and cellulose triacetate fibres and, preferably, linear polyester fibres which may also be acid-modified, and which are obtained by the conden~tion of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis(hydroxymethyl)cyclohexane, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol, or the incorporation of sulfoisophthalic acid. The linear polyester fibre material hitherto used almost exclusively in the textile industry consists of terephthalic acid and ethylene glycol.
The fibre materials may also be used as blends with each other or with other fibres, typically blends of polyacrylonitrile/polyester, polyamide/polyester, polyester/cotton, polyester/viscose and polyester/wool, and they can be dyed or also printed batchwise or continuously by known methods.
The textile material can be in different forms of presentation, preferably as piece goods 21372~2 such as knitgoods or wovens or also as yarn on cheeses, warp beams and the like.
Dyeing is carried out from an aqueous liquor by a continuous or batch process. In batchwise dyeing, the liquor ratio may be chosen over a wide range, typically from 1:4 to 1:100, preferably from 1:6 to 1:50. The dyeing teml!eralure is at least 50C and is normally not higher than 140C. The plefelled temperature range is from 80 to 135C.
In continuous dyeing methods, the dye liquors, which may contain further auxiliaries in addition to the dyes, are applied to the piece goods by padding or slop-padding and developed by thermofixation or HT ste~ming processes.
Linear polyester fibres and cellulose fibres are preferably dyed by the high temperature process in closed and pressure-resistant apparatus in the temperature range >100C, preferably in the range from 110 to 135C, and at normal or elevated pressure. Suitable closed apparatus includes typically circulation dyeing m~hines such as cheese or beam dyeing machines, winch becks, jet or drum dyeing machines, muff dyeing machines,paddles or jiggers.
For continuous dyeing, padders or lick rollers are used and development is carried out with hot air in stenter frames or in HT steamers.
Cellulose secondary acetate is preferably dyed in the temperature range from 80-85C.
When using the novel UV absorbers for dye application, the procedure is such that the fibre material is first treated with these compounds and then dyeing is carried out or, preferably, the fibre material is treated simultaneously in the dyebath with theUV absorber and the dye. The application of the UV absorber can, however, also be made subsequently to the ready prepared dyeing by padding and thermofixation, conveniently at 190-230C over a period of 30 seconds to 5 minutes.
The dye liquors may also contain further ingredients such as dyeing assistants, dispersants, diffusion accelerators, wool protectives, and wetting agents as well as antifoams.
The dyebaths may also contain mineral acids, typically sulfuric acid or phosphoric acid, or conveniently organic acids, typically aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and/or salts such as ammonium acetate, ammonium ;~3!37Z~2 sulfate or sodium acetate. The acids are used in particular to adjust the pH of the liquors used in the practice of this invention to 4-5.
Preferably the fibre material is first run over S minutes at 40-80C in the bath which contains the dye, the UV absorber and any further auxiliaries and which has been adjusted to pH 4.5-5.5. Then the temperature is raised to 125-130C over 10 to 20 minutes and further treatment is carried out for 15 to 90 minutes, preferably for 30 minutes, at this len,pc;l~ture.
The dyeings are finished by cooling the dye liquor to 50-80C, washing off the dyeings with water and, if nçcess~ry, reduction clearing them in conventional manner in ~lk~line medium. The dyeings are then again washed off and dried.
For producing prints, the novel UV absorbers are mixed in the form of aqueous dispersions with the print pastes. The print paste then contains the UV absorber in an amount of 0.5 to 5 %, preferably 1 to 2 %, based on the weight of the fibre material to be printed.
The amount of dye added to the print pastes will depend on the desired shade. Normally amounts of 0.01 to 15 % by weight, preferably of 0.02 to 10 % by weight, based on the textile material to be used, have been found useful.
In addition to containing the dyes and the aqueous dispersion of the 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 admixture with modified cellulose, preferably with 20 to 25 % by weight of carboxymethyl cellulose. The print pastes may additionally contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, sequestrants, emulsifiers, water-insoluble solvents, oxidising agents or dearators.
Particularly suitable preservatives are formaldehyde donors such as parafonn~ldehyde or trioxane, preferably c. 30 to 40 % by weight aqueous formaldehyde solutions. Suitable sequestrants are typically sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, preferably sodium polymethaphosphate, more particularly sodium hexamethaphosphate.
Emulsifiers are preferably polyadducts of an alkylene oxide and a fatty alcohol, more particularly a polyadduct of oleyl alcohol and ethylene oxide. Water-insoluble solvents are ;~3L372,~
preferably high-boiling saturated hydrocarbons, more particularly paraffins having a boiling range from about 160 to 210C (white spirits). Oxidising agents are typically aromatic nitro compounds, preferably an aromatic mono- or dinitrocarboxylic acid or mono- or dinitrosulfonic acid which may be in the form of an alkylene oxide polyadduct, preferably a nitrobenzenesulfonic acid. Deaerators are suitably high-boiling solvents, preferably terpentine oils, higher alcohols, in particular C8-Cl0alcohols, terpene alcohols or deaerators based on mineral and/or silicone oils, preferably commercial formulations comprising about 15-25 % by weight of a Illi~Ule of mineral and silicone oils and about 75-85 % by weight of a C8alcohol such as 2-ethyl-n-hexanol.
For printing the fibre materials, the print paste is applied direct to the whole or to a part of the surface, conveniently using printing machines of conventional construction, typically rotogravure, rotary screen printing and surface screen printing m~chines.
The fibre material is dried after printing in the tempeldtule range up to 150C, preferably in the range from 80 to 120C.
The subsequent fixation of the fibre material is usually carried out by a heat treatment, preferably in the temperature range from 100 to 220. The heat treatment is norm~lly carried out with superheated steam under atmospheric pressure.
Depending on the temperature, fixation is carried out for 20 seconds to 10 minutes, preferably for 4 to 8 minutes.
The prints are also finished in conventional manner by washing off with water, followed by an optional reductive afterclear in alkaline medium, conveniently with sodiumdithionite. In this last mentioned case, the prints are again washed off, hydroextracted and dried.
For transfer printing, the printing paste is coated on paper and subsequently transferred from the paper to the fibre material. Transfer printing on the calendering machine is preferably carried out at 210-240C over 20 to 60 seconds.
The process of this invention makes it possible to obtain polyester dyeings and prints of excellent fastness to light and sublimation and which are suitable for use in automobile upholstery as well as in canvas, nets and belts, but also for so-called out-door articles such ~:~37~i;2 as sun shades, sun blinds and awnings. The process of this invention requires no specific pretreatment or aftertre~tment of the fibre material. In addition, a reduction of the diffuse tr~n~mi~sion of UV radiation through textiles made from polyester fibres as well as from polyester fibre blends is achieved with the polyester fibre materials which have been treated with the compounds of formula (1).
In the following working and application Examples percentages are by weight. Theamounts of dye and UV absorbers are based on pure substance.
Preparation of the UV absorbers Exmample 1: 135 g of the compound of formula ~N~ ~ (100) OH
and 132 g of N-hydroxymethylben7~mide are homogenised and then added, with stirring, over 90 minutes at 0-5C to 660 ml of sulfuric acid (95-97%). The reaction is allowed to go to completion for 2 hours at 0-5C. The viscous, yellow solution is then poured over 20 minutes into 3000 g of a mixture of ice/water of 0-5C. The resultant pale yellow suspension is stirred for 30 minutes and filtered. Subsequently, the filter product is washed with water until neutral and then dried, giving 206 g (96% of theory) of the compound of formula HO~CH2NHCO~ (101).
The procedure of Example 1 is repeated, but using as benzotriazole a compound offormula /~N ~ , wherein R2 and R3 are as defined in Table 1, and replacing N-hydroxymethylben7~mide by an equivalent amount of a compound of formula 2~372~
Ho-cH2-R , wherein R is as defined in Table 1, to give compounds of formula ~ N~ ~ , wherein R, Rl and R3 are as defined in Table 1.
R3 OH Rl ~3~2 ~....
Table 1 Example R3 R2 R *m.p.C
3 H -CH3 -NH-CO-nC4Hg 4 H -CH3 --NH C(}~ Cl H -CH3 --NH C~CI
o 7 H -CH3 ~) 8 H -CH3 ~
9 H -CH3 o2~=
Cl Cl 14 H -CH3 - HN co{~3 H -CH3 --HN--CO--CH~ 228-230 *m.p.: melting point Example 17: The procedure of Example 1 is repeated, but using as benzotriazole acompound of formula N ~ tl05)~
OH C(CH3)3 and replacing N-hydroxymethylben7~micle with an equivalent amount of a compound of formula HO-CH2-NH-CO-CH2Cl, to give a compound of formula Cl-CH2-CO-NH-CH~ CH3 /~N ~ (106).
C O C(CH3)3 The melting point of the compound is 198-200C.
Example 18: 348.8 g of the compound of formula (100) in accordance with Example 1, 124.7 g of N-hydroxymethylbenzamide and 104.7 g of N-hydroxymethylchloroacet~mide are homogenised and then added, with stirring, over 90 minutes at 0-5C to 1700 ml of sulfuric acid (95-97%). The solution is stirred for 10 minutes at 5C, and stirring is then continued while the temperature rises to room temp~, ~lure. After 3 hours, the yellow solution is poured into c. 6000 g of a mixture of icetwater, stirred for 90 minutes and then filtered. The filter product is then washed with water until neutral and dried, giving 529 g (yield: 98% of theory) of the mixture of the compounds of formulae N HO CH2NHCO--CH~3 [~C N~ (102) and [~ N ~ (103) in the ratio of 1:1. The melting point of the mixture is 182-199C.
Example 19: In general accordance with the procedure of Example 18, 11.3 g of the compound of formula (100), 2.1 g of N-hydroxymethylbenzamide and 5.1 g of N-hydroxy-~ 7~2 methylchloroacetamide are homogenised and is then added over 25 minutes to 55 ml ofsulfuric acid (95-97%), to give, after drying, 16.3 g of the mixture of the compounds of formulae (102) and (103) in the ratio of 1:3. The melting point of the mixture is 178- 190C.
Example 20: In general accordance with the procedure of Example 18, 11.3 g of the compound of formula (100), 3.3 g of N-hydroxymethylben7~mide and 2.7g of N-hy-droxy methylchloroacetamide are homogenised and added over 25 minutes to 55 ml of sulfuric acid (95-97%), to give, after drying, 15.7 g of the mixture of the compounds of formulae (102), (103) and [~--N`N ~ (104) in the ratio of 4:4:2. The melting point of the mixture is 170-185C.
Example 21: In general accordance with the procedure of Example 18, 23.6 g of the compound of formula (100), 4.1 g of N-hydroxymethylben7~mide and 10.2 g of N-hy-droxymethylchloroacetamide are homogenised and added over 45 minutes to 110 ml of sulfuric acid (95-97%). Upon completion of the reaction, 8.3 g of the compound of formula HO C(CH3)3 N~ (105) are added to the reaction mixture. As soon as this compound has dissolved, the resnlt~nt yellow solution is immediately poured into 600 g of ice/water and stirred for 15 minutes.
The product is isolated by filtration, washed with water until neutral and then dried, giving 42.8 g of the mixture of the compounds of formulae (102), (103) and (105) in the ratio of 1:3:1. The melting point of the mixture is 160-181C.
Example 22: 5.6 g of the compound of formula (100) according to Example 1 are homogenised with 7.9 g of the compound of formula (105) and 6.8 g of N-hydroxy-methylchloroacetamide and the mixture is then added over 20 minutes to 55 ml of sulfuric ~1372~2 ....
acid (95-97%). The procedure of Example 18 is then repeated to give, after drying, 17.8 g of the mixture of the compounds of formulae (103) and HO C(CH3)3 N ~ CH3 (106) in the ratio of 1:1. The melting point of the mixture is 168-176C.
Application Examples:
Examples 23 and 24: (exhaust process) Three 10 g samples of PES tricot are dyed in a HT dyeing machine, e.g. (~)Turbomat (supplied by Mathis, Niederhasli) in the liquor ratio of 1:10. The liquors contain 2g/1 of ammonium sulfate, 0.5 g/l of a dyeing auxiliary, e.g. (~Univadin 3-flex and the dyes of formulae (1) to (IV) in the following amounts:
0.035% of the dye of formula (I) ~`NHJ~so2 0.016% of the dye of formula ~OCHzCH20COO-R
HO R= -C2H5 and phenyl in the ratio of 1:1 0.02% of the dye of formula O OH
O HN~ , and ~SO2-CH3 0.016% of the dye of formula ;~;37~2 ... .
(IV) ~N-- ~CH2)3-OCH3 (142parts) H2N O -(CH2)3-O(CH)20CH3 (58 parts) Whereas liquor 1 contains no further ingredients, the further addition of 0.75% of the compound of formula I~CNN~ (102) is made to liquor 2, and the further addition of 0.75% of the compound of formula HO~CH~NHC~ (101) is made to liquor 3 as 25% milled formulations.
Preparation of the milled formulation: 5 g of the active ingredient of the UV absorbers are milled with an impeller (1500 rpm) to a particle size of < 2 ~lm with a solution of 2.5 g of the 1Tieth~nol~mine salt of tristyrylphenylpolyethylene glycol phosphoric acid and 12.5 ml of water, with addition of 20 g of quartz balls (diameter 1 mm). The milled formulation is adjusted to 25% with water.
Liquors 1 to 3 are adjusted to pH 5 with dilute acetic acid and then dispersed intensively.
For dyeing, the liquors and tricot samples are put into pressure bombs and dyeing is commenced at 70C. After S minutes the tel"pel~ture is raised to 135C at a rate of 2C/minute. The liquor is kept for 30 minutes at 135C and then cooled to 60C.
Subsequently, the dyed goods are washed off and a reductive afterclear is carried out over 30 minutes at 70C with a solution containing 2 ml/l of sodium hydroxide 36 Bè and 3g/1 of sodium thionite. The dyed goods are then rinsed warm and cold and dried. The li~h~ tness properties are determined by irradiating the dyeings in accordance with DIN
75.202 (FAKRA) and SAE J 1885. The results are reported in Table 2.
2~37~L2 Table 2:
lightfastness determined by grey scale according to dyeing FAKRA FAKRA SAE SAE
(liquor) 4cycles 6 cycles 420KJ 600 KJ
(l? no addition 2-3 2 3-4 -3 (2) + compound (102)3-4 3 4 3-4 (3) + compound (101)3-4 3 4 3 4 Table 2 demonsllates that the use of the UV absorbers of formulae (102) and (101) m~rk~lly enh~nces the lightfastness propellies of the grey dyeings obtained.
Examples 25 and 26: (exhaust process) The procedure of Examples 2 and 3 is repeated, using the following dye combinations (liquors 4 to 6):
dye of formula I: 0.37%
dye of formula II: 0.067%
dye of formula III: 0.010%
dye of formula IV: 0.013%
The formulations of the compounds of formulae (102) and (101) are added to liquors 5 and 6. The dyeings are prepared, fini~hecl and tested for their lightfastness properties in accordance with the procedure of Examples 2 and 3. The results are reported in Table 3.
Table 3:
lightf~tness determined by grey scale according to dyeing FAKRA FAKRA SAE SAE
(liquor) 4 cycles 6 cycles 420 KJ 600 KJ
(4) no addition 2 1-2 2-3 1-2 (5)+compound (102) 3-4 -3 3-4 2-3 (6)+compound (101) 3-4 2-3 2-3 2+
Table 3 demonstrates that the use of the UV absorbers of formulae (102) and (103) m~rk~1ly enhances the lightfastness properties of the beige dyeings obtained.
2137Z~2 ..--.
Examples 27 to 30: (pad thermofixation process) Following the description of Examples 23 to 26, 3 liquors are prepared for grey dyeings, in general accordance with Examples 23 and 24, and 3 liquors for beige dyeings, in general accordance with Examples 25 and 26. For padding, each liquor contains 0.5g/1 of a dispersant such as a nonylphenol polyglycol ether having 10 ethylene oxide units. A
control dyeing (without UV absorber), a dyeing with 28 g/l of the compound of formula (102) as 25% milled formulation and a dyeing with 28 g/l of the compound of formula (101) as 25% milled formulation each are prepared for the grey dyeings as well as for the beige dyeings. Padding is carried out with a pinch-off effect of 95% and the dyed goods are dried immediately at 110C for 3 minutes and then thermofixed at 190C for 60 minutes. The lightfastness properties of the dyeings so obtained are determined according to DIN 75.202 and SAE J 1885, giving the results reported in Table 4.
Table 4:
lightfastness properties by grey scale according to grey dyeing FAKRA FAKRA SAE SAE
(liquor) 4 cycles 6 cycles 420 KJ 600 KJ
(7? no addition 3 1-2 2-3 2-3 (9)+compound (101) 4 3 4 3-4 beige dyeing (liquor) (10) no addition 2R 1 2-3R 2R
(11) + compound (102) 2-3 2 3 3 (12) + compound (101) -3 2+ 2 2-3 The ratings of the lightfastness prope, lies demonstrate that the compounds of formulae (102) and (101) may also be developed under heat fixation conditions.
Examples 31 and 32: (direct printing) Printing pastes for printing textured polyester tricot are prepared from a stock thickening, dyes and, as required, UV absorbers. The stock thickening has the following composition:
~37~;~2 .
120 g of a starch ether thickener 480 g of a sodium alginate thickener 5 g of sodium dihydrogen phosphate 5 g of sodium chlorate 5 g of a printing auxiliary (e.g. LYOPRINT AP(g)) 385 g of deionised water 1000 g of stock thickening The three printing pastes 13, 14 and 15 are mixed from components A, B and C:
A) 1.4 g of the dye of formula (I) 0.9 g of the dye of formula (II) 0.5 g of the dye of formula (III) 1.3 g of the dye of formula (IV) B) 0 g of UV absorber (paste 13), or 7.5 g of the compound of formula (102) (paste 14), or 7.5 g of the compound of formula (101) (paste 15) and C) are bulked to a total of 1000 g with stock thickening.
The compounds of formula (102) and (101) are used in the form of finely dispersed 25%
milled formulation.
The cleaned tricot pieces are printed with the above printing pastes on a printing table (supplied by Zimmer, Klagenfurt, Austria). The samples are then dried over 10 minutes at 100C and subsequently steamed over 8 minutes at 180C with superheated steam. The dyed goods are then rinsed with water and given a reductive afterclear for 30 minutes at 70C with a solution of 2 ml/l of sodium hydroxide 38Bé and 3 g/l of sodium dithionite.
Finally, the samples are rinsed thoroughly, dried at 80C and then tested for their lightfa~tness properties.
2~ 37~2 Table 5:
lightfastness in ~ E according to CIELAB, 65/10; DIN 6174 print FAKRA SAE
(paste) 5 cycles 488 KJ
(13) no addition 4.61 4.81 (14) + compound (102) 2.46 2.40 (15) + compound (101) 1.95 2.31 Table 5 demonstrates that the lightfastness properties of the prints are enh~nced by the UV absorbers of formulae (102) and (101).
o 7 H -CH3 ~) 8 H -CH3 ~
9 H -CH3 o2~=
Cl Cl 14 H -CH3 - HN co{~3 H -CH3 --HN--CO--CH~ 228-230 *m.p.: melting point Example 17: The procedure of Example 1 is repeated, but using as benzotriazole acompound of formula N ~ tl05)~
OH C(CH3)3 and replacing N-hydroxymethylben7~micle with an equivalent amount of a compound of formula HO-CH2-NH-CO-CH2Cl, to give a compound of formula Cl-CH2-CO-NH-CH~ CH3 /~N ~ (106).
C O C(CH3)3 The melting point of the compound is 198-200C.
Example 18: 348.8 g of the compound of formula (100) in accordance with Example 1, 124.7 g of N-hydroxymethylbenzamide and 104.7 g of N-hydroxymethylchloroacet~mide are homogenised and then added, with stirring, over 90 minutes at 0-5C to 1700 ml of sulfuric acid (95-97%). The solution is stirred for 10 minutes at 5C, and stirring is then continued while the temperature rises to room temp~, ~lure. After 3 hours, the yellow solution is poured into c. 6000 g of a mixture of icetwater, stirred for 90 minutes and then filtered. The filter product is then washed with water until neutral and dried, giving 529 g (yield: 98% of theory) of the mixture of the compounds of formulae N HO CH2NHCO--CH~3 [~C N~ (102) and [~ N ~ (103) in the ratio of 1:1. The melting point of the mixture is 182-199C.
Example 19: In general accordance with the procedure of Example 18, 11.3 g of the compound of formula (100), 2.1 g of N-hydroxymethylbenzamide and 5.1 g of N-hydroxy-~ 7~2 methylchloroacetamide are homogenised and is then added over 25 minutes to 55 ml ofsulfuric acid (95-97%), to give, after drying, 16.3 g of the mixture of the compounds of formulae (102) and (103) in the ratio of 1:3. The melting point of the mixture is 178- 190C.
Example 20: In general accordance with the procedure of Example 18, 11.3 g of the compound of formula (100), 3.3 g of N-hydroxymethylben7~mide and 2.7g of N-hy-droxy methylchloroacetamide are homogenised and added over 25 minutes to 55 ml of sulfuric acid (95-97%), to give, after drying, 15.7 g of the mixture of the compounds of formulae (102), (103) and [~--N`N ~ (104) in the ratio of 4:4:2. The melting point of the mixture is 170-185C.
Example 21: In general accordance with the procedure of Example 18, 23.6 g of the compound of formula (100), 4.1 g of N-hydroxymethylben7~mide and 10.2 g of N-hy-droxymethylchloroacetamide are homogenised and added over 45 minutes to 110 ml of sulfuric acid (95-97%). Upon completion of the reaction, 8.3 g of the compound of formula HO C(CH3)3 N~ (105) are added to the reaction mixture. As soon as this compound has dissolved, the resnlt~nt yellow solution is immediately poured into 600 g of ice/water and stirred for 15 minutes.
The product is isolated by filtration, washed with water until neutral and then dried, giving 42.8 g of the mixture of the compounds of formulae (102), (103) and (105) in the ratio of 1:3:1. The melting point of the mixture is 160-181C.
Example 22: 5.6 g of the compound of formula (100) according to Example 1 are homogenised with 7.9 g of the compound of formula (105) and 6.8 g of N-hydroxy-methylchloroacetamide and the mixture is then added over 20 minutes to 55 ml of sulfuric ~1372~2 ....
acid (95-97%). The procedure of Example 18 is then repeated to give, after drying, 17.8 g of the mixture of the compounds of formulae (103) and HO C(CH3)3 N ~ CH3 (106) in the ratio of 1:1. The melting point of the mixture is 168-176C.
Application Examples:
Examples 23 and 24: (exhaust process) Three 10 g samples of PES tricot are dyed in a HT dyeing machine, e.g. (~)Turbomat (supplied by Mathis, Niederhasli) in the liquor ratio of 1:10. The liquors contain 2g/1 of ammonium sulfate, 0.5 g/l of a dyeing auxiliary, e.g. (~Univadin 3-flex and the dyes of formulae (1) to (IV) in the following amounts:
0.035% of the dye of formula (I) ~`NHJ~so2 0.016% of the dye of formula ~OCHzCH20COO-R
HO R= -C2H5 and phenyl in the ratio of 1:1 0.02% of the dye of formula O OH
O HN~ , and ~SO2-CH3 0.016% of the dye of formula ;~;37~2 ... .
(IV) ~N-- ~CH2)3-OCH3 (142parts) H2N O -(CH2)3-O(CH)20CH3 (58 parts) Whereas liquor 1 contains no further ingredients, the further addition of 0.75% of the compound of formula I~CNN~ (102) is made to liquor 2, and the further addition of 0.75% of the compound of formula HO~CH~NHC~ (101) is made to liquor 3 as 25% milled formulations.
Preparation of the milled formulation: 5 g of the active ingredient of the UV absorbers are milled with an impeller (1500 rpm) to a particle size of < 2 ~lm with a solution of 2.5 g of the 1Tieth~nol~mine salt of tristyrylphenylpolyethylene glycol phosphoric acid and 12.5 ml of water, with addition of 20 g of quartz balls (diameter 1 mm). The milled formulation is adjusted to 25% with water.
Liquors 1 to 3 are adjusted to pH 5 with dilute acetic acid and then dispersed intensively.
For dyeing, the liquors and tricot samples are put into pressure bombs and dyeing is commenced at 70C. After S minutes the tel"pel~ture is raised to 135C at a rate of 2C/minute. The liquor is kept for 30 minutes at 135C and then cooled to 60C.
Subsequently, the dyed goods are washed off and a reductive afterclear is carried out over 30 minutes at 70C with a solution containing 2 ml/l of sodium hydroxide 36 Bè and 3g/1 of sodium thionite. The dyed goods are then rinsed warm and cold and dried. The li~h~ tness properties are determined by irradiating the dyeings in accordance with DIN
75.202 (FAKRA) and SAE J 1885. The results are reported in Table 2.
2~37~L2 Table 2:
lightfastness determined by grey scale according to dyeing FAKRA FAKRA SAE SAE
(liquor) 4cycles 6 cycles 420KJ 600 KJ
(l? no addition 2-3 2 3-4 -3 (2) + compound (102)3-4 3 4 3-4 (3) + compound (101)3-4 3 4 3 4 Table 2 demonsllates that the use of the UV absorbers of formulae (102) and (101) m~rk~lly enh~nces the lightfastness propellies of the grey dyeings obtained.
Examples 25 and 26: (exhaust process) The procedure of Examples 2 and 3 is repeated, using the following dye combinations (liquors 4 to 6):
dye of formula I: 0.37%
dye of formula II: 0.067%
dye of formula III: 0.010%
dye of formula IV: 0.013%
The formulations of the compounds of formulae (102) and (101) are added to liquors 5 and 6. The dyeings are prepared, fini~hecl and tested for their lightfastness properties in accordance with the procedure of Examples 2 and 3. The results are reported in Table 3.
Table 3:
lightf~tness determined by grey scale according to dyeing FAKRA FAKRA SAE SAE
(liquor) 4 cycles 6 cycles 420 KJ 600 KJ
(4) no addition 2 1-2 2-3 1-2 (5)+compound (102) 3-4 -3 3-4 2-3 (6)+compound (101) 3-4 2-3 2-3 2+
Table 3 demonstrates that the use of the UV absorbers of formulae (102) and (103) m~rk~1ly enhances the lightfastness properties of the beige dyeings obtained.
2137Z~2 ..--.
Examples 27 to 30: (pad thermofixation process) Following the description of Examples 23 to 26, 3 liquors are prepared for grey dyeings, in general accordance with Examples 23 and 24, and 3 liquors for beige dyeings, in general accordance with Examples 25 and 26. For padding, each liquor contains 0.5g/1 of a dispersant such as a nonylphenol polyglycol ether having 10 ethylene oxide units. A
control dyeing (without UV absorber), a dyeing with 28 g/l of the compound of formula (102) as 25% milled formulation and a dyeing with 28 g/l of the compound of formula (101) as 25% milled formulation each are prepared for the grey dyeings as well as for the beige dyeings. Padding is carried out with a pinch-off effect of 95% and the dyed goods are dried immediately at 110C for 3 minutes and then thermofixed at 190C for 60 minutes. The lightfastness properties of the dyeings so obtained are determined according to DIN 75.202 and SAE J 1885, giving the results reported in Table 4.
Table 4:
lightfastness properties by grey scale according to grey dyeing FAKRA FAKRA SAE SAE
(liquor) 4 cycles 6 cycles 420 KJ 600 KJ
(7? no addition 3 1-2 2-3 2-3 (9)+compound (101) 4 3 4 3-4 beige dyeing (liquor) (10) no addition 2R 1 2-3R 2R
(11) + compound (102) 2-3 2 3 3 (12) + compound (101) -3 2+ 2 2-3 The ratings of the lightfastness prope, lies demonstrate that the compounds of formulae (102) and (101) may also be developed under heat fixation conditions.
Examples 31 and 32: (direct printing) Printing pastes for printing textured polyester tricot are prepared from a stock thickening, dyes and, as required, UV absorbers. The stock thickening has the following composition:
~37~;~2 .
120 g of a starch ether thickener 480 g of a sodium alginate thickener 5 g of sodium dihydrogen phosphate 5 g of sodium chlorate 5 g of a printing auxiliary (e.g. LYOPRINT AP(g)) 385 g of deionised water 1000 g of stock thickening The three printing pastes 13, 14 and 15 are mixed from components A, B and C:
A) 1.4 g of the dye of formula (I) 0.9 g of the dye of formula (II) 0.5 g of the dye of formula (III) 1.3 g of the dye of formula (IV) B) 0 g of UV absorber (paste 13), or 7.5 g of the compound of formula (102) (paste 14), or 7.5 g of the compound of formula (101) (paste 15) and C) are bulked to a total of 1000 g with stock thickening.
The compounds of formula (102) and (101) are used in the form of finely dispersed 25%
milled formulation.
The cleaned tricot pieces are printed with the above printing pastes on a printing table (supplied by Zimmer, Klagenfurt, Austria). The samples are then dried over 10 minutes at 100C and subsequently steamed over 8 minutes at 180C with superheated steam. The dyed goods are then rinsed with water and given a reductive afterclear for 30 minutes at 70C with a solution of 2 ml/l of sodium hydroxide 38Bé and 3 g/l of sodium dithionite.
Finally, the samples are rinsed thoroughly, dried at 80C and then tested for their lightfa~tness properties.
2~ 37~2 Table 5:
lightfastness in ~ E according to CIELAB, 65/10; DIN 6174 print FAKRA SAE
(paste) 5 cycles 488 KJ
(13) no addition 4.61 4.81 (14) + compound (102) 2.46 2.40 (15) + compound (101) 1.95 2.31 Table 5 demonstrates that the lightfastness properties of the prints are enh~nced by the UV absorbers of formulae (102) and (101).
Claims (24)
1. A process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materials, which comprises treating said fibre material with at least one compound of formula (1), wherein R1 is the radical of formula (2), R2 and R'2 are each independently of the other hydrogen, C1-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and Rs is C1-C12alkyl, C1-C6monohaloalkyl, C1-C6dihaloalkyl, C1-C4alkenyl, C1-C4monohaloalkenyl, C5-C7cycloalkyl, phenyl; phenyl or phenyl-C1-C4alkyl, eachsubstituted by C1-C4alkyl, C1-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or (3c), wherein n is 1, 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen.
2. A process according to claim 1, which comprises using at least one compound of formula (4), wherein R1, R2 and R3 are as defined in claim 1.
3. A process according to claim 2, which comprises using at least one compound of formula (4), wherein R1 is the radical of formula (2), R2 is hydrogen, C1-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and R5 is C1-C12alkyl, C1-C6monohaloalkyl, C1-C6dihaloalkyl, C1-C4alkenyl, C1-C4monohaloalkenyl, C5-C7cycloalkyl, unsubstituted phenyl or phenyl which is substituted by C1-C4alkyl, C1-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or (3c), wherein n is 1, 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen.
4. A process according to either claim 1 or claim 2, which comprises using at least one compound of formula (1) or (4), wherein R1 is a radical of formula (2), R2 is hydrogen, C1-C4alkyl, C5-C7cycloalkyl, (C1-C4alkyl)phenyl, phenyl, benzyl or phenethyl, R'2 is hydrogen or C1-C4alkyl, R3 is hydrogen, chloro or bromo, R4 is hydrogen, and R5 is C1-C6alkyl, C1-C4chloroalkyl, C1-C4dichloroalkyl, C1-C4dibromoalkyl, C1-C4alkenyl, C1-C4chloroalkenyl, C1-C4bromoalkenyl, C5-C7cycloalkyl, phenyl; phenyl or benzyl, each substituted by C1-C4alkyl, C1-C4alkoxy, chloro or bromo, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or (3c), wherein n is 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl or halogen.
5. A process according to any one of claims 1 to 4, which comprises using at least one compound of formula (5), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R8 is methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl, n-butyl, phenyl, chlorophenyl, dichlorophenyl, 1,2-dichloroethyl, 1,2-dibromoethyl, cyclohexyl, 1-chlorovinyl or 1-bromovinyl.
6. A process according to either claim 1 or claim 2, which comprises using at least one compound of formula (6), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R9 is a radical of formula (3a), (3b) or (3c), wherein n is 3, R6 is hydrogen or methyl, and R7 is hydrogen.
7. A process according to claim 1, which comprises using at least one compound of formula (7), wherein R1, R2, R'2 and R3 are as defined in claim 1, and, in particular, wherein R1, R2, R'2 and R3 are as defined in claim 4.
8. A process according to claim 1, which comprises using a mixture of at least one compound of formula (1) and a compound of formula (8), wherein R2, R'2 and R3 are as defined in claim 1.
9. A process according to claim 1, which comprises using a mixture of two compounds of formula (1).
10. A process according to any one of claims 1 to 9, which comprises using the compound of formula (1) in an amount of 0.01 to 5 % by weight, based on the fibre material.
11. A process according to any one of claims 1 to 10, wherein, in the dyeing application, the compound of formula (1) is added direct to the dye bath or to the padding liquor.
12. A process according to any one of claims 1 to 10, wherein, in the printing application, the compound of formula (1) is mixed with the printing paste.
13. A compound of formula (1a), wherein R1 is the radical of formula (2a), R2 and R'2 are each independently of the other hydrogen, C1-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and R5 is C1-C12alkyl, C2-C6monohaloalkyl, C1-C6dihaloalkyl, C1-C4alkenyl, C1-C4monohaloalkenyl, C5-C7cycloalkyl, phenyl; phenyl or phenyl-C1-C4alkyl, eachsubstituted by C1-C4alkyl, C1-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a'), (3b') or (3c'), wherein n is 1, 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen, or wherein R1 is the radical of formula -CH2-N(R4)-CO-CH2-Cl, R2 is hydrogen, C2-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, R3 is hydrogen or halogen, and R4 is hydrogen or C1-C4alkyl.
14. A compound according to claim 13, of formula (4a), wherein R1, R2 and R3 are as defined in claim 13.
15. A compound according to claim 14, wherein R1 is the radical of formula (2a), R2 is hydrogen, C1-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and R5 is C1-C12alkyl, C1-C6monohaloalkyl, C1-C6dihaloalkyl, C1-C4alkenyl, C1-C4monohaloalkenyl, C5-C7cycloalkyl, unsubstituted phenyl or phenyl which is substituted by C1-C4alkyl, C1-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radcial, form a radical of formula (3a'), (3b') or (3c'), wherein n is 1, 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen.
16. A compound according to either claim 13 or claim 14, wherein R1 is the radical of formula (2a), R2 is hydrogen, C1-C4alkyl, C5-C7cycloalkyl, (C1-C4alkyl)phenyl, phenyl, benzyl or phenethyl, R'2 is hydrogen or C1-C4alkyl, R3 is hydrogen, chloro or bromo, R4 is hydrogen, and R5 is C1-C6alkyl, C2-C4chloroalkyl, C1-C4dichloroalkyl, C2-C4dibromoalkyl, C1-C4alkenyl, C1-C4chloroalkenyl, C1-C4bromoalkenyl, C5-C7cycloalkyl, phenyl; phenyl or benzyl, each substituted by C1-C4alkyl, C1-C4alkoxy, chloro or bromo, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a'), (3b') or (3c'), wherein n is 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl or halogen.
17. A compound according to any one of claims 13 to 16, of formula (5a), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R8 is methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl, n-butyl, phenyl, chlorophenyl, dichlorophenyl, 1,2-dichloroethyl, 1,2-dibromoethyl, cyclohexyl, 1-chlorovinyl or 1-bromovinyl.
18. A compound according any one of claims 13 to 16, of formula (6a), wherein R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec-butyl, tert-butyl, isobutyl or n-butyl, R3 is hydrogen or chloro, and R9 is a radical of formula (3a'), (3b') or (3c'), wherein n is 3, R6 is hydrogen or methyl, and R7 is hydrogen.
19. A compound according to either claim 13 or claim 16, of formula (7a), wherein R1, R2, R'2 and R3 are as defined in claim 13, and, in particular, wherein R1, R2, R'2 and R3 are as defined in claim 16.
20. A process for the preparation of a compound of formula (1a) according to claim 13, which comprises reacting a compound of formula (8a), wherein R2, R'2 and R3 are as defined in formula (1a), with a compound which introduces the radical of formula (2a), wherein R4 and R5 have the meanings given in formula (2a).
21. A process for the photochemical and thermal stabilisation of undyed polyester fibre materials, which comprises treating the dyeable fibre material with a dye liquorcontaining, in addition to a disperse dye, a compound of formula (1), wherein R1 is the radical of formula (2), R2 and R'2 are each independently of the other hydrogen, C1-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and R5 is C1-C12alkyl, C1-C6monohaloalkyl, C1-C6dihaloalkyl, C1-C4alkenyl, C1-C4-monohaloalkenyl, C5-C7cycloalkyl, phenyl; phenyl or phenyl-C1-C4alkyl, each substituted by C1-C4alkyl, C1-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or (3c), wherein n is 1, 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen.
22. Use of a compound as defined in claim 13 for the photochemical stabilisation of dyeable or dyed or printed polyester fibre materials.
23. A mixture comprising at least one compound of formula (1), wherein R1 is the radical of formula (2), R2 and R'2 are each independently of the other hydrogen, C1-C12alkyl, C5-C7cycloalkyl, (C1-C8alkyl)phenyl, phenyl, C7-C9phenylalkyl or C1-C4alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4alkyl, and R5 is C1-C12alkyl, C1-C6monohaloalkyl, C1-C6dihaloalkyl, C1-C4alkenyl, C1-C4monohaloalkenyl, C5-C7cycloalkyl, phenyl; phenyl or phenyl-C1-C4alkyl, each substituted by C1-C4alkyl, C1-C4alkoxy or halogen, or R4 and R5, together with the linking -N-CO- radical, form a radical of formula (3a), (3b) or (3c), wherein n is 1, 2, 3 or 4, R6 is hydrogen or C1-C4alkyl, and R7 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen.
24. A mixture according to claim 23 comprising, in addition to at least one compound of formula (1) according to claim 23, a compound of formula (8), wherein R2, R'2 and R3 are as defined in claim 23.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH362893 | 1993-12-06 | ||
| CH3628/93-1 | 1993-12-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2137212A1 true CA2137212A1 (en) | 1995-06-07 |
Family
ID=4260068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2137212 Abandoned CA2137212A1 (en) | 1993-12-06 | 1994-12-02 | Process for the photochemical and thermal stabilisation of undyed and dyed or printed polyester fibre materials |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0657577A1 (en) |
| JP (1) | JPH07196631A (en) |
| CA (1) | CA2137212A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7105479B2 (en) | 2001-03-27 | 2006-09-12 | Ciba Specialty Chemicals Corporation | Fabric rinse composition containing a benztriazole UV absorber |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291586B2 (en) * | 1996-05-03 | 2001-09-18 | 3M Innovative Properties Company | Amide functional ultraviolet light absorbers for polyurethanes and polyureas |
| US5994431A (en) * | 1996-05-03 | 1999-11-30 | 3M Innovative Properties Company | Amide functional ultraviolet light absorbers for polyolefins |
| JP5308039B2 (en) | 2007-02-20 | 2013-10-09 | 富士フイルム株式会社 | Polymer materials containing UV absorbers |
| US20100130638A1 (en) | 2007-03-30 | 2010-05-27 | Fujifilm Corporation | Ultraviolet absorbent composition |
| CN101821273A (en) | 2007-08-16 | 2010-09-01 | 富士胶片株式会社 | Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent |
| JP5244437B2 (en) | 2008-03-31 | 2013-07-24 | 富士フイルム株式会社 | UV absorber composition |
| JP5250289B2 (en) | 2008-03-31 | 2013-07-31 | 富士フイルム株式会社 | UV absorber composition |
| JP2009270062A (en) | 2008-05-09 | 2009-11-19 | Fujifilm Corp | Ultraviolet absorbent composition |
| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3394125A (en) * | 1965-10-23 | 1968-07-23 | Bristol Myers Co | 2-phenyl-3-tertiary-aminoalkoxy phenyl-and corresponding tertiaryaminoalkyl thio benzfurans substituted in the benzo nucleus with an alkoxy or tertiaryamino alkoxy or alkylthio group |
| NL6809017A (en) * | 1967-07-01 | 1969-01-03 | ||
| EP0474595B1 (en) * | 1990-08-28 | 1995-09-27 | Ciba-Geigy Ag | Aqueous dispersion of low-solubility UV-absorbers |
| DE59204472D1 (en) * | 1991-07-12 | 1996-01-11 | Ciba Geigy Ag | Process for printing and photochemical stabilization of polyester fiber materials. |
-
1994
- 1994-11-29 EP EP94810674A patent/EP0657577A1/en not_active Withdrawn
- 1994-12-02 CA CA 2137212 patent/CA2137212A1/en not_active Abandoned
- 1994-12-06 JP JP6302388A patent/JPH07196631A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7105479B2 (en) | 2001-03-27 | 2006-09-12 | Ciba Specialty Chemicals Corporation | Fabric rinse composition containing a benztriazole UV absorber |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0657577A1 (en) | 1995-06-14 |
| JPH07196631A (en) | 1995-08-01 |
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