CA2043484A1 - Stabilisation of dyeings on polyamide fibres - Google Patents
Stabilisation of dyeings on polyamide fibresInfo
- Publication number
- CA2043484A1 CA2043484A1 CA002043484A CA2043484A CA2043484A1 CA 2043484 A1 CA2043484 A1 CA 2043484A1 CA 002043484 A CA002043484 A CA 002043484A CA 2043484 A CA2043484 A CA 2043484A CA 2043484 A1 CA2043484 A1 CA 2043484A1
- Authority
- CA
- Canada
- Prior art keywords
- radical
- formula
- hydrogen
- process according
- c4alkyl
- 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
- 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
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
-
- 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
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/924—Polyamide fiber
Abstract
Stabilisation of dyeings on polyamide fibres Abstract of the disclosure Processes for improving the thermal and/or photochemical stability of undyed and dyed polyamide fibres by treatment with an agent from an aqueous bath containing (A) a compound of the formula (1) defined in claim 1 and (B) a UV absorber.
Description
8~
Stabilisation of dYeings on polvamide fibres The present invention relates to a process for improving the thermal and/or photochemical stability of undyed and dyed polyamide fibres and to the polyamide fibre material treated therewith.
The protection of ~mdyed polymers, for example polyarnides, against the effect of heat and/or oxygen (air oxidation) by means of water-soluble phenolic antioxidants is known from US-A-3 665 031. However, this protection does not satisfy today's requirements.
It has now been found that undyed and dyed polyamide fibres can be better protected by treatment with phenolic water-soluble antioxidants and UV absorbers.
Accordingly, the invention relates to a process for improving the thermal and/orphotochemical stability of undyed and dyed polyamide fibres, which comprises treating the fibres with an agent from an aqueous bath containing (A) a water-soluble compound of the formula (1) (1) (A~Y-)nz(-w)m in which A is the radical of a sterically hindered phenol from the benzene series, Y is a radical of the formulae t2) or (3) X~ N2)-~-C8--~3 (~) -(X) N (X') (X') 1~ C~
Stabilisation of dYeings on polvamide fibres The present invention relates to a process for improving the thermal and/or photochemical stability of undyed and dyed polyamide fibres and to the polyamide fibre material treated therewith.
The protection of ~mdyed polymers, for example polyarnides, against the effect of heat and/or oxygen (air oxidation) by means of water-soluble phenolic antioxidants is known from US-A-3 665 031. However, this protection does not satisfy today's requirements.
It has now been found that undyed and dyed polyamide fibres can be better protected by treatment with phenolic water-soluble antioxidants and UV absorbers.
Accordingly, the invention relates to a process for improving the thermal and/orphotochemical stability of undyed and dyed polyamide fibres, which comprises treating the fibres with an agent from an aqueous bath containing (A) a water-soluble compound of the formula (1) (1) (A~Y-)nz(-w)m in which A is the radical of a sterically hindered phenol from the benzene series, Y is a radical of the formulae t2) or (3) X~ N2)-~-C8--~3 (~) -(X) N (X') (X') 1~ C~
- 2- 2~4~3 in which X and X', independently of one another, are alkylene, oxaalkylene or thiaalkylene, R2 and R3, independently of one another, are hydrogen or a substituted or unsubstituted alkyl group and x, x' and y, independently of one another, are each O or 1, Z
is an aliphatic or a carbocyclic aromatic radical, the latter containing at most ~vo mono- or bicyclic rings, W is a sulfo group and m and n, independently of one another, are 1 or 2, and their water-soluble salts, and ~B) a UV absorber.
A in formula (1~ is, for example, a monohydroxyphenyl radical in which at least one ortho position with respect to the hydroxyl group is substituted by an alkyl, cycloall~yl or aralkyl group and which, if desired, contains further substituents.
Alkyl groups in the ortho position with respect to the hydroxyl group of A can be linear or branched and contain 1-12, preferably 4-8, C atoms. Of these, a-branched alkyl groups are preferred. They are, for example, a methyl, ethyl, isopropyl, tert-butyl, isoamyl, octyl, tert-octyl or dodecyl group. Of these, the tert-butyl group is p~rticularly preferred.
Cycloalkyl groups in the ortho position with respect to the hydroxyl group A contain 6-10, preferably 6-8, C atoms. Examples of these are the cyclohexyl, methylcyclohexyl and cyclooctyl group.
Aralkyl groups in the ortho position with respect to the hydroxyl group of A contain 7-10, preferably 8-9, C atoms. Examples of these are the a-methyl and ~ -dimethylbenzyl group.
In addition, the radical A can be substituted by further alkyl, cycloalkyl or aralkyl groups defined above, which are pre~erably in the o'- or p-position with respect to the hydroxyl group, provided these positions are not occupied by the bonding to Y. Furthermore, at least one meta position with respect to the hydroxyl group is advantageously unsubstituted, while the other can be substituted by lower alkyl groups, such as the methyl group.
Due to their easy accessibi]ity and tlleir favourable stabilising effect, compounds of the formula (1) in which A is a radical of the formula (4) ~3~
is an aliphatic or a carbocyclic aromatic radical, the latter containing at most ~vo mono- or bicyclic rings, W is a sulfo group and m and n, independently of one another, are 1 or 2, and their water-soluble salts, and ~B) a UV absorber.
A in formula (1~ is, for example, a monohydroxyphenyl radical in which at least one ortho position with respect to the hydroxyl group is substituted by an alkyl, cycloall~yl or aralkyl group and which, if desired, contains further substituents.
Alkyl groups in the ortho position with respect to the hydroxyl group of A can be linear or branched and contain 1-12, preferably 4-8, C atoms. Of these, a-branched alkyl groups are preferred. They are, for example, a methyl, ethyl, isopropyl, tert-butyl, isoamyl, octyl, tert-octyl or dodecyl group. Of these, the tert-butyl group is p~rticularly preferred.
Cycloalkyl groups in the ortho position with respect to the hydroxyl group A contain 6-10, preferably 6-8, C atoms. Examples of these are the cyclohexyl, methylcyclohexyl and cyclooctyl group.
Aralkyl groups in the ortho position with respect to the hydroxyl group of A contain 7-10, preferably 8-9, C atoms. Examples of these are the a-methyl and ~ -dimethylbenzyl group.
In addition, the radical A can be substituted by further alkyl, cycloalkyl or aralkyl groups defined above, which are pre~erably in the o'- or p-position with respect to the hydroxyl group, provided these positions are not occupied by the bonding to Y. Furthermore, at least one meta position with respect to the hydroxyl group is advantageously unsubstituted, while the other can be substituted by lower alkyl groups, such as the methyl group.
Due to their easy accessibi]ity and tlleir favourable stabilising effect, compounds of the formula (1) in which A is a radical of the formula (4) ~3~
R
(4) H ~
in which R and 1~1, independently of one another, are hydrogen, methyl or tert-butyl and the sum of the carbon atr)ms of R and Rl is at least 2 are particularly preferred.
X and X' in formulae (2) and (3) can be straight-d~ain or branched and contain 1 to 8, preferably 1 to 5, C atoms. E;;amples of these are the methylene, ethylene, trimethylene, propylene, 2-thiatrimethylene or 2-oxapenta'methylene radical.
Particular preference is given to compounds iD which two hetero atoms in radicals X and X' are not bound to the same saturated, i.e. tetr~edral, carbon atom.
Alkyl groups R2 or R3 in folmulae (2) and (3~ can be straight-chain or branched and contain 1 to 18, preferably I to 8, C atoms. E~amples of these are the methyl, ethyl, isopropyl, pentyl, octyl, dodecyl and octadecyi~ g~up.
Examples of substituted alkyl groups R2 or R3 are hydroxyalkyl, alkoxyalkyl, alTunoalkyl, alkylaminoalkyl or dialkylaminoalkyl groups h~ing a total of 2 to 10, preferably 2 to 5, C
atorns. Examples of these are the ~-hydroxyethyl, ,B-methoxyethyl"B-aminoethyl, ,B,~'-diethylaminoethyl or the ,B-butylamiTIoethyl group.
R2 or R3 can also be an aryl group, preferably a phenyl group.
Compounds in which y in formulae (2) an~3~ ~g iero in general have a substantially better stabilising effect than those compou~ids in which y is one.
Particular preferencc is given to compounds ~ d~e formula (1) in which Y is a radical of the forrnula (5) (S) -X"-C-N-2~34L~3~
in which R4 is hydrogen or Cl-C4alkyl and X" is Cl-C4alkylene.
Z in formula (1) is, for example, the radical of a lower alkane which is unsubstituted or substituted by carboxy groups and has at least two C ats)ms, the radical of a benzene ring which is unsubstituted or substituted by chlorine or bromine, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4alkoxycarbonylamino, hydroxyl, carboxy, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino, in which the group W can be bound directly to this benzene ring or to a monncyclic aryl radical of one of its substituents, or it is a naphthalene or tetraline radical.
As a radical of a lower alkane, Z can be straight-chain or branched and contain 2 to 5, preferably ~, C atoms. Thus, it is, for example, an ethylene, propylene, trimethylene or pentamethylene radical. This radical can, if desired, be additionally substituted by carboxyl groups. An example of this is the carboxyethylene radical.
As benzene radical, Z in formula (1) can be further substituted. For example, it can have straight-chain or branched Cl-C4alkyl radicals, for example it can be substituted by a methyl, ethyl or isopropyl group; of these, the methyl group is prefe~ed. Examples of Cl-C4alkoxy groups as substituents of a benzene radical Z are the methoxy, ethoxy or butoxy group. The acyl radical of Z as a benzene radical substituted by an acylamino group is derived in particular from a C2-C6aliphatic or a monocarboxylic aromatic carl)oxylic acid. Examples are the radical of acetic, propionic, ~-methoxypropionic, benzoic, aminobenzoic or methylbenzoic acid. Examples of Cl-C4alkoxycarbonylamino groups as substituen~s of a benzene radical Z are the methoxy, ethoxy or butoxycarbonylamino radical.
Phenylethyl, styryl, phenyl, phenoxy, phenylthio or phenylsulfonyl groups as substituents of group Z can be unsubstituted or substituted by chlorine or bromine, Cl-C4alkyl groups, such as the methyl or ethyl group, C1-C4alkoxy groups, such as the methoxy group, acylamino groups, such as the acetyl- or benzoylamino group or alkoxycarbonylamino groups, such as the methoxy- or ethoxycarbonylamino group.
If desired, two or more identical or different of the abovementioned substituents of the benzene radical Z or its aryl-containing substituents can be present simultaneously.
As naphthalene radical, the group Z can be unsubstituted or substituted by Cl-C4alkyl or - 5 - ~3 alkoxy groups, such as the methyl or methoxy group.
Compounds of the formula (1) in which the radical Z contains hydroxyl, amino, acylamino, alkoxycarbonylamino or styryl substituents in general show more discoloration upon exposure than compounds in which Z is free of substituents or is substituted in a different manner.
For economical reasons, compounds in which Z is an ethylene radical, a phenylene, toluylene, chlorophenylene or naphthylene radical or a divalent radical of diphenyl ether, methyl- or chlorodiphenyl ether, or in certain applications compounds in which Z is a trivalent radical of benzene or naphthalene are particularly preferred. Of these, compounds in which Z is a phenyl or diphenyl ether radical show particularly good light fastness, while compounds in which Z is a naphthyl or phenylethylphenyl radical have excellent wash fastness properties.
The sulfo group W in formula (1) is ~ee, but can also preferably be present in the form of its aLkali metal salts, alkaline earth metal salts, ammonium salt or salt of organic nitrogen bases. Owing to the low solubility of certain calcium salts, strontium salts and barium salts in water-containing media and for economical reasons, compounds of the formula (1) in which the group W is present in the form of its lithium salt, sodium salt, potassium salt, rnagnesium salt or ammonium salt or as an ammonium salt of an organic nitrogen base, the cation of which has the formula (6) (6) NR'R"R"'R""
in which R', R", R"', R"", independently of one another, are hydrogen, Cl-C4alkyl or ~-hydroxy-Cl-C4alkyl or cyclohexyl, in which at least two of these radicals can form a carbo- or heterocyclic ring system with one another, are preferred.
Examples of organic nitrogen bases which can form ammonium salts of this type with the group W are trimethylamine, triethylamine, ~iethanolamine, diethanolamine, ethanolamine, cyclohexylamine, dicyclohexylamine, hexamethyleneimine or morpholine.
Compounds of the formula (7) ~43 (7) ~;~ X"- C - N~ Z--W
have a particularly favourable stabilising effect.
In this forrnula, R and R1, independently of one another, are methyl or tert-butyl, R4 is hydrogen or Cl-C4alkyl, X" is Cl-C4alkylene, Z is an ethylene radical, a di- or trivalent radical of benzene or naphthalene or a divalent radical of diphenyl ether, W is a sulfo group and n is 1 or 2.
Group W can be present in these compounds free or also in the form of its salts defined above.
Of the compounds of the formula (7), those where R = Rl = methyl arc economically particularly favourable, while those where R = methyl and R1 = tert-butyl and in particular those where R = R1 = tert-butyl have excellent resistance to alkali.
Components (B) which may be mentioned are all UV absorbers which are described, for example, in US-A 2 777 828; 2 853 521; 3 259 627; 3 293 '247; 3 382 183; 3 403 183;
3 423 360; 4127 586; 4 230 867; 4 511596 and 4 698 064.
However, UY absorbers which have been made water-soluble are preferably suitable.
Those are described, for example, in US-A 4 141 903, 4 230 867, 4 698 064 and 4 77~ 667.
For example, the following compounds can be used:
a) 2-hydroxybenzophenones of ~he ~ormula (8) ~3~
in which R and 1~1, independently of one another, are hydrogen, methyl or tert-butyl and the sum of the carbon atr)ms of R and Rl is at least 2 are particularly preferred.
X and X' in formulae (2) and (3) can be straight-d~ain or branched and contain 1 to 8, preferably 1 to 5, C atoms. E;;amples of these are the methylene, ethylene, trimethylene, propylene, 2-thiatrimethylene or 2-oxapenta'methylene radical.
Particular preference is given to compounds iD which two hetero atoms in radicals X and X' are not bound to the same saturated, i.e. tetr~edral, carbon atom.
Alkyl groups R2 or R3 in folmulae (2) and (3~ can be straight-chain or branched and contain 1 to 18, preferably I to 8, C atoms. E~amples of these are the methyl, ethyl, isopropyl, pentyl, octyl, dodecyl and octadecyi~ g~up.
Examples of substituted alkyl groups R2 or R3 are hydroxyalkyl, alkoxyalkyl, alTunoalkyl, alkylaminoalkyl or dialkylaminoalkyl groups h~ing a total of 2 to 10, preferably 2 to 5, C
atorns. Examples of these are the ~-hydroxyethyl, ,B-methoxyethyl"B-aminoethyl, ,B,~'-diethylaminoethyl or the ,B-butylamiTIoethyl group.
R2 or R3 can also be an aryl group, preferably a phenyl group.
Compounds in which y in formulae (2) an~3~ ~g iero in general have a substantially better stabilising effect than those compou~ids in which y is one.
Particular preferencc is given to compounds ~ d~e formula (1) in which Y is a radical of the forrnula (5) (S) -X"-C-N-2~34L~3~
in which R4 is hydrogen or Cl-C4alkyl and X" is Cl-C4alkylene.
Z in formula (1) is, for example, the radical of a lower alkane which is unsubstituted or substituted by carboxy groups and has at least two C ats)ms, the radical of a benzene ring which is unsubstituted or substituted by chlorine or bromine, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4alkoxycarbonylamino, hydroxyl, carboxy, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino, in which the group W can be bound directly to this benzene ring or to a monncyclic aryl radical of one of its substituents, or it is a naphthalene or tetraline radical.
As a radical of a lower alkane, Z can be straight-chain or branched and contain 2 to 5, preferably ~, C atoms. Thus, it is, for example, an ethylene, propylene, trimethylene or pentamethylene radical. This radical can, if desired, be additionally substituted by carboxyl groups. An example of this is the carboxyethylene radical.
As benzene radical, Z in formula (1) can be further substituted. For example, it can have straight-chain or branched Cl-C4alkyl radicals, for example it can be substituted by a methyl, ethyl or isopropyl group; of these, the methyl group is prefe~ed. Examples of Cl-C4alkoxy groups as substituents of a benzene radical Z are the methoxy, ethoxy or butoxy group. The acyl radical of Z as a benzene radical substituted by an acylamino group is derived in particular from a C2-C6aliphatic or a monocarboxylic aromatic carl)oxylic acid. Examples are the radical of acetic, propionic, ~-methoxypropionic, benzoic, aminobenzoic or methylbenzoic acid. Examples of Cl-C4alkoxycarbonylamino groups as substituen~s of a benzene radical Z are the methoxy, ethoxy or butoxycarbonylamino radical.
Phenylethyl, styryl, phenyl, phenoxy, phenylthio or phenylsulfonyl groups as substituents of group Z can be unsubstituted or substituted by chlorine or bromine, Cl-C4alkyl groups, such as the methyl or ethyl group, C1-C4alkoxy groups, such as the methoxy group, acylamino groups, such as the acetyl- or benzoylamino group or alkoxycarbonylamino groups, such as the methoxy- or ethoxycarbonylamino group.
If desired, two or more identical or different of the abovementioned substituents of the benzene radical Z or its aryl-containing substituents can be present simultaneously.
As naphthalene radical, the group Z can be unsubstituted or substituted by Cl-C4alkyl or - 5 - ~3 alkoxy groups, such as the methyl or methoxy group.
Compounds of the formula (1) in which the radical Z contains hydroxyl, amino, acylamino, alkoxycarbonylamino or styryl substituents in general show more discoloration upon exposure than compounds in which Z is free of substituents or is substituted in a different manner.
For economical reasons, compounds in which Z is an ethylene radical, a phenylene, toluylene, chlorophenylene or naphthylene radical or a divalent radical of diphenyl ether, methyl- or chlorodiphenyl ether, or in certain applications compounds in which Z is a trivalent radical of benzene or naphthalene are particularly preferred. Of these, compounds in which Z is a phenyl or diphenyl ether radical show particularly good light fastness, while compounds in which Z is a naphthyl or phenylethylphenyl radical have excellent wash fastness properties.
The sulfo group W in formula (1) is ~ee, but can also preferably be present in the form of its aLkali metal salts, alkaline earth metal salts, ammonium salt or salt of organic nitrogen bases. Owing to the low solubility of certain calcium salts, strontium salts and barium salts in water-containing media and for economical reasons, compounds of the formula (1) in which the group W is present in the form of its lithium salt, sodium salt, potassium salt, rnagnesium salt or ammonium salt or as an ammonium salt of an organic nitrogen base, the cation of which has the formula (6) (6) NR'R"R"'R""
in which R', R", R"', R"", independently of one another, are hydrogen, Cl-C4alkyl or ~-hydroxy-Cl-C4alkyl or cyclohexyl, in which at least two of these radicals can form a carbo- or heterocyclic ring system with one another, are preferred.
Examples of organic nitrogen bases which can form ammonium salts of this type with the group W are trimethylamine, triethylamine, ~iethanolamine, diethanolamine, ethanolamine, cyclohexylamine, dicyclohexylamine, hexamethyleneimine or morpholine.
Compounds of the formula (7) ~43 (7) ~;~ X"- C - N~ Z--W
have a particularly favourable stabilising effect.
In this forrnula, R and R1, independently of one another, are methyl or tert-butyl, R4 is hydrogen or Cl-C4alkyl, X" is Cl-C4alkylene, Z is an ethylene radical, a di- or trivalent radical of benzene or naphthalene or a divalent radical of diphenyl ether, W is a sulfo group and n is 1 or 2.
Group W can be present in these compounds free or also in the form of its salts defined above.
Of the compounds of the formula (7), those where R = Rl = methyl arc economically particularly favourable, while those where R = methyl and R1 = tert-butyl and in particular those where R = R1 = tert-butyl have excellent resistance to alkali.
Components (B) which may be mentioned are all UV absorbers which are described, for example, in US-A 2 777 828; 2 853 521; 3 259 627; 3 293 '247; 3 382 183; 3 403 183;
3 423 360; 4127 586; 4 230 867; 4 511596 and 4 698 064.
However, UY absorbers which have been made water-soluble are preferably suitable.
Those are described, for example, in US-A 4 141 903, 4 230 867, 4 698 064 and 4 77~ 667.
For example, the following compounds can be used:
a) 2-hydroxybenzophenones of ~he ~ormula (8) ~3~
(8) R3~ ~ R
in which Rl is hydrogen, hydroxyl, C1-C14alkoxy or phenoxy, R2 is hydrogen, halogen, Cl-C4alkyl or sulfo, R3 is hydrogen, hydroxyl or Cl-C4alkoxy and R4 is hydrogen,hydroxyl or carboxy, b) 2-(2'-hydroxyphenyl)benzotriazoles of the formula (9) OH Rl R4~ \N ~ R2 in which Rl is hyclrogen, chlorine, sulfo, Cl-Cl2alkyl, C5-C6cycloalkyl, (Cl-C8alkyl)phenyl, C7-Cgphenylalkyl or sulfonated C7-C9phenylalkyl, R2 is hydrogen, chlorine, Cj-C4alkyl, C1-C4alkoxy, hydroxyl or sulfo, R3 is Cl-CI2alkyl, chlorine, sul~o, Cl-C4alkoxy, phenyl, (Cl-C8aLkyl)phenyl, Cs-C6cycloalkyl, C2-Cgalkoxycarbonyl, carboxyethyl, C7-Cgphenylalkyl or sulfonated C7-C9phenylalkyl, R4 is hydrogen, chlorine, C1-C4alkyl, Cl-C4alkoxy, C2-Cgalkoxycarbonyl, carboxy or sulfo and R~ is hydrogen or chlorine, c) 2-(2'-hydroxyphenyl)-s-triazines of the formula (10) \~N ~
(10) R>-- R Rl in which R is hydrogen, halogen, Cl-C4alkyl or sulfo, R1 is hydrogen, C1-C4alkyl, Cl-C4alkoxy or hydroxyl, R2 is hydrogen or sulfo and R3 and R4, independently of one - 8~ 39 another, are Cl-C4alkyl, Cl-C4alkoxy, Cs-C6cycloalkyl, phenyl or phenyl substitllted by Cl-C4alkyl andlor hydroxyl, and d) s-triazine compounds of the formula (11) ~1 N~N
(1 1) R21N~R3 in which at least one of the substituents Rl, R2 and R3 is a radical of the formula ( 1 2) ~3 0--A--SO3(M) I
HO
in which A is C3-C4aLkylene or 2-hydroxytrimethylene and M is sodium, potassium,calciurn, magnesium, ammonium or tetra-C1-C4aLIcylammonium and m is 1 or 2, and the remaining substituent or the remaining substituents are, independently of one another, Cl-CI2alkyl, phenyl, Cl-Cl2alkyl which is bound to the triazinyl radical via oxygen, sulfur, imino or Cl-CIlalkylimino, or are phenyl or a radical of the formula (12), for example the potassium salt of the compound of the formula (11), in which Rl is phenyl and R2 and R3 are each the radical of the forrnula (12) or the sodium salt of the compound of the formula (11), in which Rl is p-chlorophenyl and R2 and R3 are each the radical of the formula (12).
In formulae (8) to (12), Cl-C4alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl; Cl-C4alkoxy is, for example, methoxy, ethoxy, propoxy or n-butoxy; Cl-Cl4alkoxy is, for example, methoxy, ethoxy, propoxy, n-butoxy, octyloxy, dodecyloxy or tetradecyloxy; Cl-CI2alkyl is, for example, e~hyl, amyl, tert-octyl, n-dc~ecyl and preferably methyl, sec-butyl or tert-butyl; C2-Cgalkoxycarbonyl is, for example, ethoxycarbonyl, n-octoxycarbonyl or preferably methoxycarbonyl;
Cs-C6cycloalkyl is, for example, cyclopentyl or cyclohexyl; (Cl-C~alkyl)phenyl is, for example, methylphenyl, tert-butylphenyl, tert-amylphenyl or tert-octylphenyl;
C7-Cgphenylalkyl is, for example, benzyl, a-methylbenzyl or preferably 3~
g a,o~-dimethylbenzyl~ and Cl-Cllalkylimino is, for example, me~hyl-, ethyl-, butyl-, hexyl-, octyl-, decyl- or undecylimino.
The carboxy and sulfo groups can be present in the free form or salt ~orm, for example as alkali metal salts, alkaline earth metal salts, ammonium or amine salts.
The water-soluble compounds of the formula (1) are known, for exarnple from US-A 3 665 031 and can be prepared by methods known per se, ~orexample by ~eacting n mol of a compound of the formula (13) (13) A~(X)x~P
with one mol of a compound of the forrnula (14) (14) ¦w~ ~(x )x~Q]n~
in which formulae one of P and Q is the group -NH-R3, the other is the group tl~co~
V, in the case where y is 1, is the group -OAr, in the case where y is 0, a chlorine or bromine atom or a reactive amino group, in which Ar is an aromatic radical of the benzene or naphthalene series with elimination of HV.
Examples of starting materials of the formula (15) (15) A-(X)X-NH-R3 in which A, X, x and R3 are as dçfined above, which fall under the formula (13) and are suitable for preparing the water-soluble compounds according to the invention are:
4-hydroxy-3,5-di-tert-butylaniline, 4-hydroxy-3,5-di-tert-butylbenzylarnineg ~-(4-hydroxy-3,5-di-tert-butylphenyl)propylamine, 4-hydroxy-3-tert-butyl-5-methylaniline, 4-hydroxy-3,5-dicyclohexylaniline, 4-hydroxy-3,5-di-tert-amylaniline, 4-hycEroxy-3,5-di-cyclohexylbenzylamine, 4-hydroxy-3-methylcyclohexyl-5-methylaniline, 4~3 2-hydroxy-3-a,(x-dime~hylbenzyl-5-methylbenzylamine, 4-hydroxy-3,5-dibenzylaniline, ~-(4-hydroxy-3,5-dibenzylphenyl)propylamine, 2-hydroxy-3-tert-butyl-5-dodecylaniline, 4-hydroxy-3-tert-octyl-5-methylbenzylamine, 4-hydroxy-3,5-diisopropylbenzylamine, 4-hydroxy-3-tert-butyl-6-1nethylbenzylamine, 4-hydroxy-3,5-di-tert-amylbenzylamine, 2-hydroxy-3,5-dimethylaniline and 2-hydroxy-3-tert-butyl-5-methylbenzylamine.
Examples of starting materials of the formula (16) (1~) A-(X)~N7~COV
in which A, X, x, R2, y and V are as defined above and which fall uoder the formula (13) are:
,B-~4-hydroxy-3,5-di-tert-butylphenyl)-propionyl chloride, 4-hydroxy-3,5-di-tert-butyl-phenylacetyl chloride, 4-hydroxy-3,5-di-tert-butyl benzoyl chloride, 4-hydroxy-3-tert-butyl-5-methylphenylacetyl chloride, 2-hydroxy-3,5-dimethylbenzoyl chloride, 2-hydroxy-3-tert-butyl-5-methylbenzoyl chloride, S-(4-hydroxy-3-ter~-butyl-5-methyl-benzyl)thioglycolyl chloride, 4-hydroxy-5-tert-butylphenylacetyl chloride, ~-(4-hydroxy-3,5-dicyclohexylphenyl)propionyl bromide, (4-hydroxy-3,5-dicyclohexylphenyl)acetyl chloride"B-(4-hydloxy-3-benzyl-~-methylphenyl)propionyl chloride, (4-hydroxy-3-benzyl-5-methylphenyl~acetyl chloride, 4-hydroxy-3,5-di-isopropylphenylacetyl chloride, S-(4-hydroxy-3,5-diisopropylbenzyl)thioglycolyl chloride, ~ ~-(4-hydroxy-3,5-di-tert-butylphenyl)propyloxy]propionyl chloride, [~(4-hydroxy-3,5-di-tert-butylphenyl)propyloxy]acetyl chloride, ,B-methyl-~-(4-hydroxy-3,5-di-tert-butyl-phenyl)propionyl chloride, 4-hydroxy-3,5-di-tert-amylbenzyloxyacetyl chloride, and 4-hydroxy-5-tert-butyl-3-ethylbenzyloxyacetyl chloride.
Examples of starting materials of the formula (17) (17) [W~Z~(X')x~-NE~-R3]n in which W, m, Z, X', x', R3 and n are as deflned above and which fall under the formula (14), are:
2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonicacid, 5-chlor-2-aminobenzenesulfonic acid, 5-methyl-4-chloro-2-amirlobenzenesulfonic acid, 2-chloro-5-aminobenzenesulfonic acid, 4-chloro-3-aminobenzenesulfonic acid, S-chlor-3-methyl-3-aminobenzenesulfonic acid, 2,5-dichloro-~aminobenzenesulfonicacid, 3-bromo-6-aminobenzenesulfonic acid, 3,4-dichloro-6-aminobenzenesulfonic acid, 1-aminotetraline-4-sulfonic acid., 1-aminobenzene-2,5-disulfon}c acidr l-aminobenzene-2,4-disulfonic acid, 1,3-diaminobenzene-4-slllfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 2-amino-S-methyl'oenzenesulfonic acid, 5-amino-2,4-dimethylbenzenesulfonic acid, 4-amino-2-methylbenzenesulfonic acid, 3-amino-S-isopropyl-2-methylbenzenesulfonic acid, 2-amino-4,5 dimethylbenzene-sulfonic acid, 2-amino-4,5-dimethoxybenzenesulfonic acid, 5-ar~in~2-methylbenzene-sulfonic acid, 2-amino-S-ethylbenzenesulfonic acid, 1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-S-sul~oni~ acid, 1-amino-naphthalene-6-sulfonic acid, l-aminonaphthalene-7-sulfonic acid, 1-aminonaphthalene-8-sulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 2-amino-naphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-3,~disulfonic acid, 1-amino-naphthalene-3,8-disulfonic acid, 2-aminonaphthalene-4,~-disulfonic acid, 1,4-diamino-naphthalene-6-sulfonic acid, 3-amino-4-methoxybenzenesulfonic acid, 1-amino-2-methoxynaphthalene-6-sulfonic acid, 3-amino-4-hydroxybenzenesul~onic acid, 3-amino-~-hydroxybenzene-1,5-disulfonic acid, 2-amino-S-hydroxynaphthalene-7-sulfonic acid, 2-acetamido-5-aminobenzenesulfonic acid, 2-amino-S-(p-aminobenzoylamino)benzene-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-amino-5-benzamidobenzenesulfonic acid, 4,4'-diamino-2,2'-disulfodiphenylthioether, 2-amino-4-carboxy-S-chlorobenzenesulfonic acid, 4-amino-3-carboxy-benzenesulfonic acid, 5-amino-3-sulfosalicylic acid, 2-(~-phenylethyl)-5-amino-benzene-sulfonic acid, 1,2-bis[4-amino-2-sulfophenyl]ethane, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4-aminostilbene-2-sulfonic acid, 4,4'-diamino-2'-methoxystilbene-2-sulfonic acid, 4-amino-3-sulfodiphenyl ether, 2-amino-4-sulfodiphenyl e~her, 2-amino~
2'-methyl-4-sul~odiphenyl ether, 2-amino-4-chloro-4'-amyl-5-sulfodiphenyl ether,2-amino-4,4'-dichloro-2'-sulfodiphenyl ether, 2-amino-4'-methyl~sulfodiphenyl sulfone, 2,5-diamino-2'-methyl-4-sulfodiphenyl ether, benzidine-2,2'-disulfonic acid, 3,3'-di-methylbenzidine-6-sulfonic acid, benzidine-2-sulfonic acid, 2'-a~rnno-3-sulfodiphenyl sulfone, 5'-amino-2'-methyl-3-sulfodiphenyl sul~one, 2',5'-diamino-4-methyl-3-sulfodi-phenyl sulfone, 3'-amino-4'-hydroxy-3-sulfodiphenyl sulfone, 3,3'-di-amino-4,4'-disulîodiphenyl sulfone, N-ethylanilin-4-sulfonic acid, N-methyl-2-naphthyl-amine-7-sulfonic acid, 2-aminoethanesulfonic acid, N-methyl-.-ethyl-, -propyl-, -isopropyl-, -amyl-, -hexyl-, -cyclohexyl-, -octyl-, -phenyl-, -dodecyl- or-stearyl-2-aminoethanesulfonic acid, 2-methyl-2-aminoethanesulfonic acid, ~an~inopropanesulfonic acid, ~-aminobu~anesulfonic acid, c3-aminopentanesulfonic acid, N-methyl-~-an~no-propanesulfonic acid, 1,2-diaminoethanesulfonic acid, 2-methylaminopropanesulfonic acid and 2-amino-2-carboxyethanesulfonic acid.
Examples of starting materials of the formula (18) ~ IR~
(18) [W~Z~(X )X~N~COV~n in which W, m, Z, X', x', R2, y, V and n are as defined above and which fall under the formula (14), are: 2-sulfoben~oyl chloride, 3-sulfobenzoyl chloride, 4-sulfobenzoyl chloride, 3,5-disulfobenzoyl chloride, 3-sulfophthaloyl chloride, 3,4-disulfophthaloyl chloride, 4-sulfophenylacetyl chloride"B-(4-sulfophenyl~propionyl chloride, 3-sulfo-6-methylbenzoyl chloride.
Some of the abovementioned starting materials are known and can be prepared by methods known per se.
The preparation of the compounds of the formula (1) usable according to the ;nvention is described in more detail in US-A 3 665 031.
Examples of suitable compounds of the forrnula (1) usable according to the invention are compounds of the formula (19) i ~X--C-- ¦ Z--503M
in which R, lRI, R4, X and 2;-SO3M have the following meanings . _ ~ a ~ O
O . __ O c~ A
..
; - -,i~ ~
O o ~ ~
~3~3 ..... ,~
.. . ~ ~
- - -~ ~ y ~ ;
E~
3~
, .~
~ ~ ~ .
`,;'',' C~ . _ ~ ~ a~ 8 ~ ~ O O ~ ~ O
~ ~ O ~ ~
~ ~
_ ~ _ ~Y ~
_ .... ..... ~.. .___.. . . _ .
_~ ~ ~
g . , . ~
, -2~3~
. . . ~ _ ~ C,~ o o C~
~4 o .
.
~ X Z X Z X
e ~ ~ 1~1 ~U~ 0O~
_ _ _ X ~
' ~
~_ ~ ~
~ , . ._ _. _ _ E--~ ~ ~ ~ ~
~ . _ _ _. _ _ _ C~
_, .. .
~ ~ A A ~ A
, : _ X ~ ~ ~
~1. "
~ C~
_ . ~_.. .
_~ ~ ~
C ..... __ ~v__. , .~ ~ ~ ~
tC~ .. ...~ .
a~ ~ ~ tx~ a~ O ~
D ( J ~ ~ ~`I -2~3 __ .
C~ _ _ ~ o o . _ ~
1 5 ~
~ ~3 ~3 ~ ~ ~ X ~ ~
_ . . .. ..
.. _ _ f_ ~
s .~ C`~
3 ~Y
~ E c o _ ~ ~ O
,~E C
~ _____ _ _ _ ~ " I rr~
~ ~ X t~ ~
P~
D~ . ~
_ C~o .
3~
- 19~
r~ ~ A
__ .
~ `~
~ ~ X ~ ~
Z
~ X'J~
X ~
Cî ~Y~
- L~ J
- 20 - ~gL3 a _ a A ~ O O
-- ~ -~~0 --~ ~
a ~ 1~
2~4~
and the compounds of the formulae Sa N(C2Hs)3 (45) HO ~ NH--CO~
and ~max 284 nm X OH
~ CO--NH~ SO3H
(46) ~=/ >=<
C~1 m.p. 190C
The compounds of the formulae (8) and (9) can be prepared by processes known per se, such as described in US-A 3 403 183 and US-A 4 127 586.
The compounds of the ~ormula (10) can be prepared in a manner known per se, for example by the processes described in US-A 3 259 627, 3 293 247, 3 423 360 and 4 698 064.
The compounds of the formula (11) can be prepared by processes known per se, such as described in US-A 3 444 164 or EP-A 165 608.
The compositions used in the process according to the invention contain components (A) and (B) in an amount of 0.01 to 10, preferably 0.2 to 2 % by weight in a weight ratio of (A):(B) of 95:5 to 5:95, preferably 60:40 to 40:60, always calculated relative to the material to be dyed.
Application can take place before, during or after dyeing by the exhaust method or a continuous process. Application during dyeing is preferred.
In the exhaust method, the liquor ratio can be selected within a wide range, for example ~3a~
3:1 to 200:1, preferably 10:1 to 40:1. Advantageously, the process is carried out at a temperature of 20 to 120C, preferably 40 to 100C.
In the continuous process, the amount of liquor applied is advantageously 40-700, preferably ~0-500, % by weight. The fibre material is r~ivn subjected to a heat treatment in order to fix the dyes and antioxidants applied. This fixing can also be carried out by the cold pad-batch method.
The heat treatment is preferably carried out by a steaming process with treatment in a steamer using steam, which may be superheated7 at a temperature of 98 to 10~C for a period of, for example, 1-7, preferably 1-5, minutes. Fixing of the dyes by the cold pad-batch method can be carried out by storing the impregnated and preferably uprolled material at room temperature ( 15 to 30C), for example for 3 to 24 hours, the cold pad-batch time being dependent, as is known, on the dye.
After the dyeing process and the fixing are complete, the dyeings produced are washed in the usual manner and dried.
Undyed and dyed fibre materials having good thermal and/or photochemical stability are obtained by the method of the present invention.
Dyeings to be stabilised according to the invention are those which are produced by disperse, acid or metal complex dyes, in particular azo, 1:2 metal complex dyes, for example 1:2 chromium, 1:2 cobalt complex dyes or copper complex dyes.
Examples of these dyes are described in (~olour Index, 3rd edition, 1971, volume 4.
Polyamide materials are understood to mean synthe~ic polyamide, for example nylon~6, nylon-6,6 or nylon-12, and modified polyamide, for example polyamide which can be coloured under basic conditions. Apart from the pure polyamide fibres, in particular ~1bre blends made of polyurethane and polyamide are also suitable, for example knitted material made of polyamide/polyurethane in a blend ratio of 70:30. In general, the pure polyamide material or the blend can be present in a wide range of processing forms, for example as fibre, yarn, woven, knitted, nonwoven or pile fabric.
In particular dyeings on polyamide material which is exposed to light and/or heat and 2~3~8~
present, for example, as carpets or automobile upholstery fabric are particularly suitable for being treated by the present process.
The examples which follow illustrate the invention. Parts and percentages are by weight.
Example 1: Three 10 g samples of nylon-6 knitwear are dyed, for example, in a (~Zeltex Vistracolor dyeing apparatus at a liquor ratio of 30:1. For this puIpose, 3 liquors are prepared containing 0.5 g/l of monosodium phosphate and 1.5 g/l of disodium phosphate (= pH 7) and 0.2 % of the dye of the formula SO3Na ~3 N--SO~ H(~7 (100) C~l3 ~ =< (Red) N--N ~
y N!H2 in dissolved form. Liquor (1) does not receive any further addition, whereas liquor (2) receives 1 % of the compound of the formula y (101) H~}CH2 CH2 CONH~
7~ SO3Na and liquor (3) 1 % of the compollnd (101) and additionally 1 % of the compound of the formula (102), always relative to the material to be dyed.
- 24 - ;~
NaO3S ~
~ OH
(102) N~N
~3,1~N
Dyeing is started at 40C, maintaining this te ;nperature for 10 minutes~ and the liquor is then heated to 95C within 30 minutes. After a dyeing time of 20 minutes at 95C, 2 % of acetic acid (80 %) is added to each liquor and dyeing is continued for another 30 minutes The liquor is then coolecl to 70C, and the samples are rinsed, centrifuged and dried at The dyeings are tested for light fastness according to SN-ISO 105-B0~ ~Xenon) and DIN 75202 (Fakra). To test the photochemical stability of the fibre material, samples are exposed according to DIN 75202 for 216 hours alld tested for tear strength and elongation according to SN 19$.461.
Results:
Dyeing Light fastness *Tear strength~elongation XENON FAKRA 72 h after 216 h FAKR~
16-7 1-2 13.4/38.4 %
26-7 3-~ 65.6l63.3 %
3- 7 3-4 74.8l~3.8 %
*unexposed dyeings as standard These results show that compounds (101) and (102) give the dyeings not only photochemical but also the~nal protection.
Example 2: 3 dyeings (4), (5) and (6) are produced as described in Example 1, except that the following 1:2 metal complex dye of the formula (200) 8~
HO
(200) ~ N _ N ~ (bordeaux) CH3ocH2cH2NHso2 1:2 cobalt complex is used.
Testing gave the follo~ing result:
Dyeing Light ~astness*Tear strength/elongation XENON FAKRA 72 hafter 216 h FAKRA
_ 7 2 15.8/39.6 %
7 3-4 56.8n~.8 %
6 7 4 75.7/83.8 %
~unexposed dyeings as standard It can be seen that the use of compounds (101) and (102) lead to an improvement in photochemical stability.
Example 3: Two 10 g samples of a nylon knitted fabric are dyed, for example, in a (~)Zeltex Visllacolor dyeing apparatus at a liquor ratio of 30:1. For this purpose, 2 dyeing liquors containing 0.5 g/l of monosodium phosphate and 1.5 g/l of disodium phosphate (= pH 7) and 0.04 % of tbe dye comprising 2~ 8~;
-- OH HO
NaO3S ~N=N~
/ ~ ~
81 % ~ OH HO
L~ N = N
1:2 chromium complex 02NJ~--N N ~
1:2 cobalt complex and 7 % of surface-active substances, 0.û02 % of the dye of the formula (200) and 1 % of the compound (300) H~3CH CH~CCNH~350 Na are used.
Dyeing liquor 2 additionally contains 1 % of the compound of the formula HO CH(CH3)Cz~9 (301 ) ~X ~N----~
SO3Na Dyeing and testing is carried out as described in E~cample 1. The results can be seen from the table below.
Dyeing Light fastness *Tear streng~fel~gation XENON FAKRA 72 h after 216 h F~
1 7-8 3+ 56.3/-7Q.5 2 7-8 ~ 4 70.9/8Z.7 *untreated samples are standard Example 4: Three 20 g samples of a nylon-66 automo~le carpet (abowt 850 g/m2; total pile thickness = 5.5/7 mm) are dyed in a pot-type dyeing apparatus, for example a Labomat~) (from Mathis) at a liquor ratio of 20:1 (as described in Example 3).
Liquor 1 does not contain any further additive, liq~or~contains 1 % of the compoand of the form~Jla (400) HO ,~ CHzCH2CONH~SO3Na while 1 % of compound (400) and 0.75 % of cornpound (102) are added to liquor 3. All compounds are calculated Ielative to the weight of the carpet sample and added to the dyeing liquor in dissolved form.
The dyeing process is carried out as described in ~x~rnple 1.
2~ 8 The finished dyeings are, on the one hand, exposed in order to determine their light fastness according to DIN 75.202 (= Pakra) and, on the other hand, exposed as samples of 4.5 x 12 cm for 360 hours according to DIN 75.202 for the Martindale abrasion test (SN
198.529).
The results obtained are summarised in the table below:
Dyeing LIGHT FASTNESS MARTINDALE ABRASION TES~
FAKRA 144 h FAKRA 288 h Weight loss Thickness loss ._ _ _ 1.1 1 24 % 45%
2.2-3 1-2 8.4% 24%
3.- 3 2-3 5.3 % 17 %
The results show that the carpet dyeing using compound (400) is significantly stabilised, although it can be improved once again by combination with the UV absorber.
Example 5: Three 10 g samples of a nylon-66/Lycra(~ knitted fabric (80:20) are dyed with 0.2 % of dye (100) as described in Example 1. Liquor 1 does not receive any further additives. 1 % of compound (300) is added to liquor 2 in dissolved fonn and 1 % of compound (300) and 0.75 % of compound (102) are added to liquor 3.
The light fastness and photochemical stability of the dyeings is also determined as described in Example 1. The following results were obtained:
DYI~li`lG LIGHT FASTNESS TEAR STRENGTH / ELONGATION
FAKRA 72 h after exposure for 144 h according to Fakra __ . .
1. 1-2 5.6/29.2 %
2. 2 46.0/59.4 %
3. 3 60.9 / 75.~ %
These results show that the use s~f compounds (300) causes an improvement in photochemical stability, which is improved once again by combination with compound (102).
Examples 6-10: 6 10 g samples of a nylon-6 knitted fabAc are dyed according to Example 3 and dyed and filnished by the process described in Example 1, except that the following U~ absorbers are added, and then tested for light fastness according to SN-ISO 105-B02 (Xenon) and DIN 75.202 (Fakra).
The following compounds are used in the amounts shown in the table:
O-CH2-CI H-CH2-SO3Na ~H2-ClH-CH2-SO3Na N~\N N~N
~N'J~3 ~N
(61)0) (601) O-CH2-CH-CH2-SO3Na O-CH2-CH2-CH2-S03K
?OH C3~OH
H,CJ~ ~`CH~
(602) (603) HO CH(CH~)~3 SO3Na (604~ ~X N ~
CH(CH3)2--~3 SO3Na The results of the light fastness evaluations can be seen from the table below.
LIGHT FASTNE~SS
Sample No. Addition to the dyeing Xenon Fakra 144 h Fakra 216 ~r 0 no addition 6-7I H 1 H ~
1 + 1 % of compound (3()0~ 6-7 3-4 2-3 j.
2 + 1 % of compound (300) 7 4-5 4 + 0.75 % of compound (600) 3 + 1 % of compound (300) 7 4 3-4 ,~
+ 0.75 % of compound (601) 4 ~ 1 % of compound (300) 7 4-5 4 + 0.75 % of compound (602) ~.
+ 1 % of compound (300) 7 4-5 4 + 0.75 % of compound (603) 6 + 1 % of compound (300) 7 4 3 _ ~ 0.75 % of compound (604~ .
It can be seen that the additional use of the compounds of the fo~rnulae (600) to (604 leads to an improvement in hot light fastness properties.
Examples 11-15: Twelve 10 g samples of a nylon-6 knitted fabric are dyed and tested as described in E~xamples 6-10, except that the compounds listed in the table are used in th~
amounts mentioned.
48~
(605) HO~ CH2-cH2~ -cH2-cH2-so3Na 7~, (606) 3 cH cH2coNH cH~so N~
(607) H~3NH8~ +NEI((~H5)3 /
(608) HO~ CH2 CH2-C-7~CH2-CH~3 ~=~ O H ~
7~ SO3Na 2~3 . . .___ __ LIGHT FASTNESS
Dyeing No. Addition to the dyeing Xenon Fakra 144 h Fak~a 216 h .. ~ ._._ 1 no addition 6-7 1 H 1 H
2 + 0.75 V/O of compound (600) 7 2 1-2 3 + 1.00 % of compound (400) 7 2-3 2 4 + 1.00 % + 0.75 % of compound 7 4 3 (400)+(600) + 1.00 % of compound (605) 7 2-3 1-2 6 + 1.00 % + 0.75 % of cornpound 7 3-4 2-3 (605)+(600) 7 + 1.00 % of compound (606) 7 3-4 3 8 + 1.00 % + 0.75 % of compound 7 4 3-4 (606)+(600) 9 + 1.00 % of compound (607) 7 4 3-4 + 1.00 % + 0.75 % of compound 7 4-5 4 (607)+(600) 11 + 1.00 % of compound (608) 7 3-4 2-3 12 + 1.00 % + 0.75 % of compound 7 4-5 4 (608)+(600) __ These results show that the combination of phenolic antioxidants with UV absorbers, for example those of the formula (600), always leads to an improvement in hot light fastness properties.
in which Rl is hydrogen, hydroxyl, C1-C14alkoxy or phenoxy, R2 is hydrogen, halogen, Cl-C4alkyl or sulfo, R3 is hydrogen, hydroxyl or Cl-C4alkoxy and R4 is hydrogen,hydroxyl or carboxy, b) 2-(2'-hydroxyphenyl)benzotriazoles of the formula (9) OH Rl R4~ \N ~ R2 in which Rl is hyclrogen, chlorine, sulfo, Cl-Cl2alkyl, C5-C6cycloalkyl, (Cl-C8alkyl)phenyl, C7-Cgphenylalkyl or sulfonated C7-C9phenylalkyl, R2 is hydrogen, chlorine, Cj-C4alkyl, C1-C4alkoxy, hydroxyl or sulfo, R3 is Cl-CI2alkyl, chlorine, sul~o, Cl-C4alkoxy, phenyl, (Cl-C8aLkyl)phenyl, Cs-C6cycloalkyl, C2-Cgalkoxycarbonyl, carboxyethyl, C7-Cgphenylalkyl or sulfonated C7-C9phenylalkyl, R4 is hydrogen, chlorine, C1-C4alkyl, Cl-C4alkoxy, C2-Cgalkoxycarbonyl, carboxy or sulfo and R~ is hydrogen or chlorine, c) 2-(2'-hydroxyphenyl)-s-triazines of the formula (10) \~N ~
(10) R>-- R Rl in which R is hydrogen, halogen, Cl-C4alkyl or sulfo, R1 is hydrogen, C1-C4alkyl, Cl-C4alkoxy or hydroxyl, R2 is hydrogen or sulfo and R3 and R4, independently of one - 8~ 39 another, are Cl-C4alkyl, Cl-C4alkoxy, Cs-C6cycloalkyl, phenyl or phenyl substitllted by Cl-C4alkyl andlor hydroxyl, and d) s-triazine compounds of the formula (11) ~1 N~N
(1 1) R21N~R3 in which at least one of the substituents Rl, R2 and R3 is a radical of the formula ( 1 2) ~3 0--A--SO3(M) I
HO
in which A is C3-C4aLkylene or 2-hydroxytrimethylene and M is sodium, potassium,calciurn, magnesium, ammonium or tetra-C1-C4aLIcylammonium and m is 1 or 2, and the remaining substituent or the remaining substituents are, independently of one another, Cl-CI2alkyl, phenyl, Cl-Cl2alkyl which is bound to the triazinyl radical via oxygen, sulfur, imino or Cl-CIlalkylimino, or are phenyl or a radical of the formula (12), for example the potassium salt of the compound of the formula (11), in which Rl is phenyl and R2 and R3 are each the radical of the forrnula (12) or the sodium salt of the compound of the formula (11), in which Rl is p-chlorophenyl and R2 and R3 are each the radical of the formula (12).
In formulae (8) to (12), Cl-C4alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl; Cl-C4alkoxy is, for example, methoxy, ethoxy, propoxy or n-butoxy; Cl-Cl4alkoxy is, for example, methoxy, ethoxy, propoxy, n-butoxy, octyloxy, dodecyloxy or tetradecyloxy; Cl-CI2alkyl is, for example, e~hyl, amyl, tert-octyl, n-dc~ecyl and preferably methyl, sec-butyl or tert-butyl; C2-Cgalkoxycarbonyl is, for example, ethoxycarbonyl, n-octoxycarbonyl or preferably methoxycarbonyl;
Cs-C6cycloalkyl is, for example, cyclopentyl or cyclohexyl; (Cl-C~alkyl)phenyl is, for example, methylphenyl, tert-butylphenyl, tert-amylphenyl or tert-octylphenyl;
C7-Cgphenylalkyl is, for example, benzyl, a-methylbenzyl or preferably 3~
g a,o~-dimethylbenzyl~ and Cl-Cllalkylimino is, for example, me~hyl-, ethyl-, butyl-, hexyl-, octyl-, decyl- or undecylimino.
The carboxy and sulfo groups can be present in the free form or salt ~orm, for example as alkali metal salts, alkaline earth metal salts, ammonium or amine salts.
The water-soluble compounds of the formula (1) are known, for exarnple from US-A 3 665 031 and can be prepared by methods known per se, ~orexample by ~eacting n mol of a compound of the formula (13) (13) A~(X)x~P
with one mol of a compound of the forrnula (14) (14) ¦w~ ~(x )x~Q]n~
in which formulae one of P and Q is the group -NH-R3, the other is the group tl~co~
V, in the case where y is 1, is the group -OAr, in the case where y is 0, a chlorine or bromine atom or a reactive amino group, in which Ar is an aromatic radical of the benzene or naphthalene series with elimination of HV.
Examples of starting materials of the formula (15) (15) A-(X)X-NH-R3 in which A, X, x and R3 are as dçfined above, which fall under the formula (13) and are suitable for preparing the water-soluble compounds according to the invention are:
4-hydroxy-3,5-di-tert-butylaniline, 4-hydroxy-3,5-di-tert-butylbenzylarnineg ~-(4-hydroxy-3,5-di-tert-butylphenyl)propylamine, 4-hydroxy-3-tert-butyl-5-methylaniline, 4-hydroxy-3,5-dicyclohexylaniline, 4-hydroxy-3,5-di-tert-amylaniline, 4-hycEroxy-3,5-di-cyclohexylbenzylamine, 4-hydroxy-3-methylcyclohexyl-5-methylaniline, 4~3 2-hydroxy-3-a,(x-dime~hylbenzyl-5-methylbenzylamine, 4-hydroxy-3,5-dibenzylaniline, ~-(4-hydroxy-3,5-dibenzylphenyl)propylamine, 2-hydroxy-3-tert-butyl-5-dodecylaniline, 4-hydroxy-3-tert-octyl-5-methylbenzylamine, 4-hydroxy-3,5-diisopropylbenzylamine, 4-hydroxy-3-tert-butyl-6-1nethylbenzylamine, 4-hydroxy-3,5-di-tert-amylbenzylamine, 2-hydroxy-3,5-dimethylaniline and 2-hydroxy-3-tert-butyl-5-methylbenzylamine.
Examples of starting materials of the formula (16) (1~) A-(X)~N7~COV
in which A, X, x, R2, y and V are as defined above and which fall uoder the formula (13) are:
,B-~4-hydroxy-3,5-di-tert-butylphenyl)-propionyl chloride, 4-hydroxy-3,5-di-tert-butyl-phenylacetyl chloride, 4-hydroxy-3,5-di-tert-butyl benzoyl chloride, 4-hydroxy-3-tert-butyl-5-methylphenylacetyl chloride, 2-hydroxy-3,5-dimethylbenzoyl chloride, 2-hydroxy-3-tert-butyl-5-methylbenzoyl chloride, S-(4-hydroxy-3-ter~-butyl-5-methyl-benzyl)thioglycolyl chloride, 4-hydroxy-5-tert-butylphenylacetyl chloride, ~-(4-hydroxy-3,5-dicyclohexylphenyl)propionyl bromide, (4-hydroxy-3,5-dicyclohexylphenyl)acetyl chloride"B-(4-hydloxy-3-benzyl-~-methylphenyl)propionyl chloride, (4-hydroxy-3-benzyl-5-methylphenyl~acetyl chloride, 4-hydroxy-3,5-di-isopropylphenylacetyl chloride, S-(4-hydroxy-3,5-diisopropylbenzyl)thioglycolyl chloride, ~ ~-(4-hydroxy-3,5-di-tert-butylphenyl)propyloxy]propionyl chloride, [~(4-hydroxy-3,5-di-tert-butylphenyl)propyloxy]acetyl chloride, ,B-methyl-~-(4-hydroxy-3,5-di-tert-butyl-phenyl)propionyl chloride, 4-hydroxy-3,5-di-tert-amylbenzyloxyacetyl chloride, and 4-hydroxy-5-tert-butyl-3-ethylbenzyloxyacetyl chloride.
Examples of starting materials of the formula (17) (17) [W~Z~(X')x~-NE~-R3]n in which W, m, Z, X', x', R3 and n are as deflned above and which fall under the formula (14), are:
2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonicacid, 5-chlor-2-aminobenzenesulfonic acid, 5-methyl-4-chloro-2-amirlobenzenesulfonic acid, 2-chloro-5-aminobenzenesulfonic acid, 4-chloro-3-aminobenzenesulfonic acid, S-chlor-3-methyl-3-aminobenzenesulfonic acid, 2,5-dichloro-~aminobenzenesulfonicacid, 3-bromo-6-aminobenzenesulfonic acid, 3,4-dichloro-6-aminobenzenesulfonic acid, 1-aminotetraline-4-sulfonic acid., 1-aminobenzene-2,5-disulfon}c acidr l-aminobenzene-2,4-disulfonic acid, 1,3-diaminobenzene-4-slllfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 2-amino-S-methyl'oenzenesulfonic acid, 5-amino-2,4-dimethylbenzenesulfonic acid, 4-amino-2-methylbenzenesulfonic acid, 3-amino-S-isopropyl-2-methylbenzenesulfonic acid, 2-amino-4,5 dimethylbenzene-sulfonic acid, 2-amino-4,5-dimethoxybenzenesulfonic acid, 5-ar~in~2-methylbenzene-sulfonic acid, 2-amino-S-ethylbenzenesulfonic acid, 1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-S-sul~oni~ acid, 1-amino-naphthalene-6-sulfonic acid, l-aminonaphthalene-7-sulfonic acid, 1-aminonaphthalene-8-sulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 2-amino-naphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-3,~disulfonic acid, 1-amino-naphthalene-3,8-disulfonic acid, 2-aminonaphthalene-4,~-disulfonic acid, 1,4-diamino-naphthalene-6-sulfonic acid, 3-amino-4-methoxybenzenesulfonic acid, 1-amino-2-methoxynaphthalene-6-sulfonic acid, 3-amino-4-hydroxybenzenesul~onic acid, 3-amino-~-hydroxybenzene-1,5-disulfonic acid, 2-amino-S-hydroxynaphthalene-7-sulfonic acid, 2-acetamido-5-aminobenzenesulfonic acid, 2-amino-S-(p-aminobenzoylamino)benzene-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-amino-5-benzamidobenzenesulfonic acid, 4,4'-diamino-2,2'-disulfodiphenylthioether, 2-amino-4-carboxy-S-chlorobenzenesulfonic acid, 4-amino-3-carboxy-benzenesulfonic acid, 5-amino-3-sulfosalicylic acid, 2-(~-phenylethyl)-5-amino-benzene-sulfonic acid, 1,2-bis[4-amino-2-sulfophenyl]ethane, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4-aminostilbene-2-sulfonic acid, 4,4'-diamino-2'-methoxystilbene-2-sulfonic acid, 4-amino-3-sulfodiphenyl ether, 2-amino-4-sulfodiphenyl e~her, 2-amino~
2'-methyl-4-sul~odiphenyl ether, 2-amino-4-chloro-4'-amyl-5-sulfodiphenyl ether,2-amino-4,4'-dichloro-2'-sulfodiphenyl ether, 2-amino-4'-methyl~sulfodiphenyl sulfone, 2,5-diamino-2'-methyl-4-sulfodiphenyl ether, benzidine-2,2'-disulfonic acid, 3,3'-di-methylbenzidine-6-sulfonic acid, benzidine-2-sulfonic acid, 2'-a~rnno-3-sulfodiphenyl sulfone, 5'-amino-2'-methyl-3-sulfodiphenyl sul~one, 2',5'-diamino-4-methyl-3-sulfodi-phenyl sulfone, 3'-amino-4'-hydroxy-3-sulfodiphenyl sulfone, 3,3'-di-amino-4,4'-disulîodiphenyl sulfone, N-ethylanilin-4-sulfonic acid, N-methyl-2-naphthyl-amine-7-sulfonic acid, 2-aminoethanesulfonic acid, N-methyl-.-ethyl-, -propyl-, -isopropyl-, -amyl-, -hexyl-, -cyclohexyl-, -octyl-, -phenyl-, -dodecyl- or-stearyl-2-aminoethanesulfonic acid, 2-methyl-2-aminoethanesulfonic acid, ~an~inopropanesulfonic acid, ~-aminobu~anesulfonic acid, c3-aminopentanesulfonic acid, N-methyl-~-an~no-propanesulfonic acid, 1,2-diaminoethanesulfonic acid, 2-methylaminopropanesulfonic acid and 2-amino-2-carboxyethanesulfonic acid.
Examples of starting materials of the formula (18) ~ IR~
(18) [W~Z~(X )X~N~COV~n in which W, m, Z, X', x', R2, y, V and n are as defined above and which fall under the formula (14), are: 2-sulfoben~oyl chloride, 3-sulfobenzoyl chloride, 4-sulfobenzoyl chloride, 3,5-disulfobenzoyl chloride, 3-sulfophthaloyl chloride, 3,4-disulfophthaloyl chloride, 4-sulfophenylacetyl chloride"B-(4-sulfophenyl~propionyl chloride, 3-sulfo-6-methylbenzoyl chloride.
Some of the abovementioned starting materials are known and can be prepared by methods known per se.
The preparation of the compounds of the formula (1) usable according to the ;nvention is described in more detail in US-A 3 665 031.
Examples of suitable compounds of the forrnula (1) usable according to the invention are compounds of the formula (19) i ~X--C-- ¦ Z--503M
in which R, lRI, R4, X and 2;-SO3M have the following meanings . _ ~ a ~ O
O . __ O c~ A
..
; - -,i~ ~
O o ~ ~
~3~3 ..... ,~
.. . ~ ~
- - -~ ~ y ~ ;
E~
3~
, .~
~ ~ ~ .
`,;'',' C~ . _ ~ ~ a~ 8 ~ ~ O O ~ ~ O
~ ~ O ~ ~
~ ~
_ ~ _ ~Y ~
_ .... ..... ~.. .___.. . . _ .
_~ ~ ~
g . , . ~
, -2~3~
. . . ~ _ ~ C,~ o o C~
~4 o .
.
~ X Z X Z X
e ~ ~ 1~1 ~U~ 0O~
_ _ _ X ~
' ~
~_ ~ ~
~ , . ._ _. _ _ E--~ ~ ~ ~ ~
~ . _ _ _. _ _ _ C~
_, .. .
~ ~ A A ~ A
, : _ X ~ ~ ~
~1. "
~ C~
_ . ~_.. .
_~ ~ ~
C ..... __ ~v__. , .~ ~ ~ ~
tC~ .. ...~ .
a~ ~ ~ tx~ a~ O ~
D ( J ~ ~ ~`I -2~3 __ .
C~ _ _ ~ o o . _ ~
1 5 ~
~ ~3 ~3 ~ ~ ~ X ~ ~
_ . . .. ..
.. _ _ f_ ~
s .~ C`~
3 ~Y
~ E c o _ ~ ~ O
,~E C
~ _____ _ _ _ ~ " I rr~
~ ~ X t~ ~
P~
D~ . ~
_ C~o .
3~
- 19~
r~ ~ A
__ .
~ `~
~ ~ X ~ ~
Z
~ X'J~
X ~
Cî ~Y~
- L~ J
- 20 - ~gL3 a _ a A ~ O O
-- ~ -~~0 --~ ~
a ~ 1~
2~4~
and the compounds of the formulae Sa N(C2Hs)3 (45) HO ~ NH--CO~
and ~max 284 nm X OH
~ CO--NH~ SO3H
(46) ~=/ >=<
C~1 m.p. 190C
The compounds of the formulae (8) and (9) can be prepared by processes known per se, such as described in US-A 3 403 183 and US-A 4 127 586.
The compounds of the ~ormula (10) can be prepared in a manner known per se, for example by the processes described in US-A 3 259 627, 3 293 247, 3 423 360 and 4 698 064.
The compounds of the formula (11) can be prepared by processes known per se, such as described in US-A 3 444 164 or EP-A 165 608.
The compositions used in the process according to the invention contain components (A) and (B) in an amount of 0.01 to 10, preferably 0.2 to 2 % by weight in a weight ratio of (A):(B) of 95:5 to 5:95, preferably 60:40 to 40:60, always calculated relative to the material to be dyed.
Application can take place before, during or after dyeing by the exhaust method or a continuous process. Application during dyeing is preferred.
In the exhaust method, the liquor ratio can be selected within a wide range, for example ~3a~
3:1 to 200:1, preferably 10:1 to 40:1. Advantageously, the process is carried out at a temperature of 20 to 120C, preferably 40 to 100C.
In the continuous process, the amount of liquor applied is advantageously 40-700, preferably ~0-500, % by weight. The fibre material is r~ivn subjected to a heat treatment in order to fix the dyes and antioxidants applied. This fixing can also be carried out by the cold pad-batch method.
The heat treatment is preferably carried out by a steaming process with treatment in a steamer using steam, which may be superheated7 at a temperature of 98 to 10~C for a period of, for example, 1-7, preferably 1-5, minutes. Fixing of the dyes by the cold pad-batch method can be carried out by storing the impregnated and preferably uprolled material at room temperature ( 15 to 30C), for example for 3 to 24 hours, the cold pad-batch time being dependent, as is known, on the dye.
After the dyeing process and the fixing are complete, the dyeings produced are washed in the usual manner and dried.
Undyed and dyed fibre materials having good thermal and/or photochemical stability are obtained by the method of the present invention.
Dyeings to be stabilised according to the invention are those which are produced by disperse, acid or metal complex dyes, in particular azo, 1:2 metal complex dyes, for example 1:2 chromium, 1:2 cobalt complex dyes or copper complex dyes.
Examples of these dyes are described in (~olour Index, 3rd edition, 1971, volume 4.
Polyamide materials are understood to mean synthe~ic polyamide, for example nylon~6, nylon-6,6 or nylon-12, and modified polyamide, for example polyamide which can be coloured under basic conditions. Apart from the pure polyamide fibres, in particular ~1bre blends made of polyurethane and polyamide are also suitable, for example knitted material made of polyamide/polyurethane in a blend ratio of 70:30. In general, the pure polyamide material or the blend can be present in a wide range of processing forms, for example as fibre, yarn, woven, knitted, nonwoven or pile fabric.
In particular dyeings on polyamide material which is exposed to light and/or heat and 2~3~8~
present, for example, as carpets or automobile upholstery fabric are particularly suitable for being treated by the present process.
The examples which follow illustrate the invention. Parts and percentages are by weight.
Example 1: Three 10 g samples of nylon-6 knitwear are dyed, for example, in a (~Zeltex Vistracolor dyeing apparatus at a liquor ratio of 30:1. For this puIpose, 3 liquors are prepared containing 0.5 g/l of monosodium phosphate and 1.5 g/l of disodium phosphate (= pH 7) and 0.2 % of the dye of the formula SO3Na ~3 N--SO~ H(~7 (100) C~l3 ~ =< (Red) N--N ~
y N!H2 in dissolved form. Liquor (1) does not receive any further addition, whereas liquor (2) receives 1 % of the compound of the formula y (101) H~}CH2 CH2 CONH~
7~ SO3Na and liquor (3) 1 % of the compollnd (101) and additionally 1 % of the compound of the formula (102), always relative to the material to be dyed.
- 24 - ;~
NaO3S ~
~ OH
(102) N~N
~3,1~N
Dyeing is started at 40C, maintaining this te ;nperature for 10 minutes~ and the liquor is then heated to 95C within 30 minutes. After a dyeing time of 20 minutes at 95C, 2 % of acetic acid (80 %) is added to each liquor and dyeing is continued for another 30 minutes The liquor is then coolecl to 70C, and the samples are rinsed, centrifuged and dried at The dyeings are tested for light fastness according to SN-ISO 105-B0~ ~Xenon) and DIN 75202 (Fakra). To test the photochemical stability of the fibre material, samples are exposed according to DIN 75202 for 216 hours alld tested for tear strength and elongation according to SN 19$.461.
Results:
Dyeing Light fastness *Tear strength~elongation XENON FAKRA 72 h after 216 h FAKR~
16-7 1-2 13.4/38.4 %
26-7 3-~ 65.6l63.3 %
3- 7 3-4 74.8l~3.8 %
*unexposed dyeings as standard These results show that compounds (101) and (102) give the dyeings not only photochemical but also the~nal protection.
Example 2: 3 dyeings (4), (5) and (6) are produced as described in Example 1, except that the following 1:2 metal complex dye of the formula (200) 8~
HO
(200) ~ N _ N ~ (bordeaux) CH3ocH2cH2NHso2 1:2 cobalt complex is used.
Testing gave the follo~ing result:
Dyeing Light ~astness*Tear strength/elongation XENON FAKRA 72 hafter 216 h FAKRA
_ 7 2 15.8/39.6 %
7 3-4 56.8n~.8 %
6 7 4 75.7/83.8 %
~unexposed dyeings as standard It can be seen that the use of compounds (101) and (102) lead to an improvement in photochemical stability.
Example 3: Two 10 g samples of a nylon knitted fabric are dyed, for example, in a (~)Zeltex Visllacolor dyeing apparatus at a liquor ratio of 30:1. For this purpose, 2 dyeing liquors containing 0.5 g/l of monosodium phosphate and 1.5 g/l of disodium phosphate (= pH 7) and 0.04 % of tbe dye comprising 2~ 8~;
-- OH HO
NaO3S ~N=N~
/ ~ ~
81 % ~ OH HO
L~ N = N
1:2 chromium complex 02NJ~--N N ~
1:2 cobalt complex and 7 % of surface-active substances, 0.û02 % of the dye of the formula (200) and 1 % of the compound (300) H~3CH CH~CCNH~350 Na are used.
Dyeing liquor 2 additionally contains 1 % of the compound of the formula HO CH(CH3)Cz~9 (301 ) ~X ~N----~
SO3Na Dyeing and testing is carried out as described in E~cample 1. The results can be seen from the table below.
Dyeing Light fastness *Tear streng~fel~gation XENON FAKRA 72 h after 216 h F~
1 7-8 3+ 56.3/-7Q.5 2 7-8 ~ 4 70.9/8Z.7 *untreated samples are standard Example 4: Three 20 g samples of a nylon-66 automo~le carpet (abowt 850 g/m2; total pile thickness = 5.5/7 mm) are dyed in a pot-type dyeing apparatus, for example a Labomat~) (from Mathis) at a liquor ratio of 20:1 (as described in Example 3).
Liquor 1 does not contain any further additive, liq~or~contains 1 % of the compoand of the form~Jla (400) HO ,~ CHzCH2CONH~SO3Na while 1 % of compound (400) and 0.75 % of cornpound (102) are added to liquor 3. All compounds are calculated Ielative to the weight of the carpet sample and added to the dyeing liquor in dissolved form.
The dyeing process is carried out as described in ~x~rnple 1.
2~ 8 The finished dyeings are, on the one hand, exposed in order to determine their light fastness according to DIN 75.202 (= Pakra) and, on the other hand, exposed as samples of 4.5 x 12 cm for 360 hours according to DIN 75.202 for the Martindale abrasion test (SN
198.529).
The results obtained are summarised in the table below:
Dyeing LIGHT FASTNESS MARTINDALE ABRASION TES~
FAKRA 144 h FAKRA 288 h Weight loss Thickness loss ._ _ _ 1.1 1 24 % 45%
2.2-3 1-2 8.4% 24%
3.- 3 2-3 5.3 % 17 %
The results show that the carpet dyeing using compound (400) is significantly stabilised, although it can be improved once again by combination with the UV absorber.
Example 5: Three 10 g samples of a nylon-66/Lycra(~ knitted fabric (80:20) are dyed with 0.2 % of dye (100) as described in Example 1. Liquor 1 does not receive any further additives. 1 % of compound (300) is added to liquor 2 in dissolved fonn and 1 % of compound (300) and 0.75 % of compound (102) are added to liquor 3.
The light fastness and photochemical stability of the dyeings is also determined as described in Example 1. The following results were obtained:
DYI~li`lG LIGHT FASTNESS TEAR STRENGTH / ELONGATION
FAKRA 72 h after exposure for 144 h according to Fakra __ . .
1. 1-2 5.6/29.2 %
2. 2 46.0/59.4 %
3. 3 60.9 / 75.~ %
These results show that the use s~f compounds (300) causes an improvement in photochemical stability, which is improved once again by combination with compound (102).
Examples 6-10: 6 10 g samples of a nylon-6 knitted fabAc are dyed according to Example 3 and dyed and filnished by the process described in Example 1, except that the following U~ absorbers are added, and then tested for light fastness according to SN-ISO 105-B02 (Xenon) and DIN 75.202 (Fakra).
The following compounds are used in the amounts shown in the table:
O-CH2-CI H-CH2-SO3Na ~H2-ClH-CH2-SO3Na N~\N N~N
~N'J~3 ~N
(61)0) (601) O-CH2-CH-CH2-SO3Na O-CH2-CH2-CH2-S03K
?OH C3~OH
H,CJ~ ~`CH~
(602) (603) HO CH(CH~)~3 SO3Na (604~ ~X N ~
CH(CH3)2--~3 SO3Na The results of the light fastness evaluations can be seen from the table below.
LIGHT FASTNE~SS
Sample No. Addition to the dyeing Xenon Fakra 144 h Fakra 216 ~r 0 no addition 6-7I H 1 H ~
1 + 1 % of compound (3()0~ 6-7 3-4 2-3 j.
2 + 1 % of compound (300) 7 4-5 4 + 0.75 % of compound (600) 3 + 1 % of compound (300) 7 4 3-4 ,~
+ 0.75 % of compound (601) 4 ~ 1 % of compound (300) 7 4-5 4 + 0.75 % of compound (602) ~.
+ 1 % of compound (300) 7 4-5 4 + 0.75 % of compound (603) 6 + 1 % of compound (300) 7 4 3 _ ~ 0.75 % of compound (604~ .
It can be seen that the additional use of the compounds of the fo~rnulae (600) to (604 leads to an improvement in hot light fastness properties.
Examples 11-15: Twelve 10 g samples of a nylon-6 knitted fabric are dyed and tested as described in E~xamples 6-10, except that the compounds listed in the table are used in th~
amounts mentioned.
48~
(605) HO~ CH2-cH2~ -cH2-cH2-so3Na 7~, (606) 3 cH cH2coNH cH~so N~
(607) H~3NH8~ +NEI((~H5)3 /
(608) HO~ CH2 CH2-C-7~CH2-CH~3 ~=~ O H ~
7~ SO3Na 2~3 . . .___ __ LIGHT FASTNESS
Dyeing No. Addition to the dyeing Xenon Fakra 144 h Fak~a 216 h .. ~ ._._ 1 no addition 6-7 1 H 1 H
2 + 0.75 V/O of compound (600) 7 2 1-2 3 + 1.00 % of compound (400) 7 2-3 2 4 + 1.00 % + 0.75 % of compound 7 4 3 (400)+(600) + 1.00 % of compound (605) 7 2-3 1-2 6 + 1.00 % + 0.75 % of cornpound 7 3-4 2-3 (605)+(600) 7 + 1.00 % of compound (606) 7 3-4 3 8 + 1.00 % + 0.75 % of compound 7 4 3-4 (606)+(600) 9 + 1.00 % of compound (607) 7 4 3-4 + 1.00 % + 0.75 % of compound 7 4-5 4 (607)+(600) 11 + 1.00 % of compound (608) 7 3-4 2-3 12 + 1.00 % + 0.75 % of compound 7 4-5 4 (608)+(600) __ These results show that the combination of phenolic antioxidants with UV absorbers, for example those of the formula (600), always leads to an improvement in hot light fastness properties.
Claims (17)
1. A process for improving the thermal and/or photochemical stability of undyed and dyed polyamide fibres, which comprises treating the fibres with an agent from an aqueous bath containing (A) a water-soluble compound of the formula (1) (A-Y-)nZ(-W)m in which A is the radical of a sterically hindered phenol from the benzene series, Y is a radical of the formulae (2) or (3) (2) (3) in which X and X', independently of one another, are alkylene, oxaalkylene or thiaalkylene, R2 and R3, independently of one another, are hydrogen or a substituted or unsubstituted alkyl group and x, x' and y, independently of one another, are each 0 or 1, Z
is an aliphatic or a carbocyclic aromatic radical, the latter containing at most two mono- or bicyclic rings, W is a sulfo group and m and n, independently of one another, are 1 or 2, and their water-soluble salts, and (B) a UV absorber.
is an aliphatic or a carbocyclic aromatic radical, the latter containing at most two mono- or bicyclic rings, W is a sulfo group and m and n, independently of one another, are 1 or 2, and their water-soluble salts, and (B) a UV absorber.
2. A process according to claim 1, wherein component (A) used is a compound of the formula (1) in which A is a monohydroxyphenyl radical in which at least one o position with respect to the hydroxyl group is substituted by alkyl having 1-12 C atoms, cycloalkyl having 6-10 C atoms or aralkyl having 7-10 C atoms and which, if desired, carries further substituents.
3. A process according to either of claims 1 or 2, wherein component (A) used is a compound of the formula (1) in which A is a radical of the formula (4) (4) in which R and R1, independently of one another, are hydrogen, methyl or tert-butyl and the sum of the carbon atoms of R and R1 is at least 2.
4. A process according to any one of claims 1 to 3, wherein X and X' in the compounds of the formulae (2) and (3) are straight-chain or branched alkylene having 1-8 C atoms.
5. A process according to any one of claims 1 to 4, wherein R2 and R3 in the compounds of the formulae (2) and (3) are straight-chain or branched C1-C8alkyl.
6. A process according to either of claims 1 or 4, wherein R2 and R3 in the compounds of the formulae (2) and (3) are hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl each having a total of 2-10 C atoms or are phenyl.
7. A process according to claim 1, wherein Y in formula (1) is a radical of the formula (5) (5) in which R4 is hydrogen or C1-C4alkyl and X" is C1-C4alkylene.
8. A process according to any one of claims 1 to 7, wherein Z in formula (1) is the radical of an unsubstituted or carboxy-substituted alkane having at least 2 C atoms, the radical of a benzene ring which is unsubstituted or substituted by chlorine or bromine, C1-C4alkyl, C1-C4alkoxy, C1-C4alkoxycarbonylamino, hydroxyl, carboxy, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino, in which the group W can be bound directly to this benzene ring or to a monocyclic aryl radical of one of its substituents, or it is a naphthalene or tetraline radical.
9. A process according to claim 1, wherein component (A) used is a compound of the formula (7) (7) in which R and R1, independently of one another, are methyl or tert-butyl, R4 is hydrogen or C1-C4alkyl, X" is C1-C4alkylene, Z is an ethylene radical, a di- or trivalent radical of benzene or naphthalene or a divalent radical of diphenyl ether, W is a sulfo group and n is 1 or 2.
10. Process according to claim 9, whcrein component (A) used is a compound of the folmula (7) in which R and Rl are tert-butyl, X" is methylene or ethylene, R4 is hydrogen, methyl or ethyl and Z is ethylene, o-, m- or p-phenylene, 1,4-naphthylene, 1,8-naphthylene, 2-methoxy-1,6-naphthylene, 1,5-naphthylene, 2,5-naphthylene, 2,6-naphthylene, 1,4,6-naphthalenetriyl or the radicals in which the sulfo group W is present in the form of its alkali metal salts or ammonium salts.
11. A process according to any one of claims 1 to 10, wherein component (B) used is a 2-hydroxybenzophenone of the formula (8) in which R1 is hydrogen, hydroxyl, C1-C14alkoxy or phenoxy, R2 is hydrogen, halogen, C1-C4alkyl or sulfo, R3 is hydrogen, hydroxyl or C1-C4alkoxy and R4 is hydrogen,hydroxyl or carboxy.
12. A process according to any one of claims 1 to 10, wherein component (B) used is a 2-(2'-hydroxyphenyl)benzotriazole of the formula (9) in which R1 is hydrogen, chlorine, sulfo, C1-C12alkyl, C5-C6cycloalkyl, (C1-C8alkyl)phenyl, C7-C9phenylalkyl or sulfonated C7-C9phenylalkyl, R2 is hydrogen, chlorine, C1-C4alkyl, C1-C4alkoxy, hydroxyl or sulfo, R3 is C1-C12alkyl, chlorine, sulfo, C1-C4alkoxy, phenyl, (C1-C8alkyl)phenyl, C5-C6cycloalkyl, C2-C9alkoxycarbonyl, carboxyethyl, C7-Cgphenylalkyl or sulfonated C7-CgphenylalkyL R4 is hydrogen, chlorine, C1-C4alkyl, C1-C4alkoxy, C2-C9alkoxycarbonyl, carboxy or sulfo and R5 is hydrogen or chlorine.
13. A process according to any one of claims 1 to 10, wherein component (B) used is a 2-(2'-hydroxyphenyl)-s-triazine of the formula (10) in which R is hydrogen, halogen, C1-C4alkyl or sulfo, R1 is hydrogen, C1-C4alkyl, C1-C4alkoxy or hydroxyl, R2 is hydrogen or sulfo and R3 and R4, independently of one another, are C1-C4alkyl, C1-C4alkoxy, C5-C6cycloalkyl, phenyl or phenyl substituted by C1-C4alkyl and/or hydroxyl.
14. A process according to any one of claims 1 to 10, wherein component (B) used is an s-triazine compound of the formula (11) in which at least one of the substituents R1, R2 and R3 is a radical of the formula (12) in which A is C3-C4alkylene or 2-hydroxytrimethylene and M is sodium, potassium,calcium, magnesium, ammonium or tetra-C1-C4alkylammonium and m is 1 or 2, and the remaining substituent or the remaining substituents are, independently of one another, C1-C12alkyl, phenyl, C1-C12alkyl which is bound to the triazinyl radical via oxygen, sulfur, imino or C1-C11alkylimino, or are phenyl or a radical of the formula (12).
15. A process according to any one of claims 1 to 14, wherein the composition is applied to the fibres by the exhaust rnethod or a continuous process.
16. A process according to any one of claims 1 to 15 for improving the thermal and/or photochemical stability of polyamide fibres dyed with disperse, acid or metal complex dyes.
17. An undyed or dyed polyamide fibre treated by the process according to claim 1.
FD 4.1/PR/bg*
FD 4.1/PR/bg*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH184390 | 1990-05-31 | ||
| CH1843/90-7 | 1990-05-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2043484A1 true CA2043484A1 (en) | 1991-12-01 |
Family
ID=4219910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002043484A Abandoned CA2043484A1 (en) | 1990-05-31 | 1991-05-29 | Stabilisation of dyeings on polyamide fibres |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5181935A (en) |
| EP (1) | EP0459950B1 (en) |
| JP (1) | JP3051494B2 (en) |
| CA (1) | CA2043484A1 (en) |
| DE (1) | DE59108599D1 (en) |
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|---|---|---|---|---|
| CH688013B5 (en) * | 1992-09-08 | 1997-10-31 | Ciba Geigy Ag | Stabilization of dyeings on polyamide fibers. |
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| US5773182A (en) | 1993-08-05 | 1998-06-30 | Kimberly-Clark Worldwide, Inc. | Method of light stabilizing a colorant |
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| US5733693A (en) | 1993-08-05 | 1998-03-31 | Kimberly-Clark Worldwide, Inc. | Method for improving the readability of data processing forms |
| JP2705895B2 (en) * | 1993-12-28 | 1998-01-28 | 大阪精化工業株式会社 | Treatment agent for textile materials |
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| DE59509122D1 (en) * | 1994-08-25 | 2001-05-03 | Ciba Sc Holding Ag | Water-soluble piperidine triazine compounds and their use for stabilizing polyamide fibers |
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| US5855655A (en) | 1996-03-29 | 1999-01-05 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
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| US5782963A (en) | 1996-03-29 | 1998-07-21 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5891229A (en) | 1996-03-29 | 1999-04-06 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| US5834544A (en) * | 1997-10-20 | 1998-11-10 | Uniroyal Chemical Company, Inc. | Organic materials stabilized by compounds containing both amine and hindered phenol functional functionalities |
| BR9906513A (en) | 1998-06-03 | 2001-10-30 | Kimberly Clark Co | New photoinitiators and applications for the same |
| JP2002517540A (en) | 1998-06-03 | 2002-06-18 | キンバリー クラーク ワールドワイド インコーポレイテッド | Neo nanoplast and microemulsion technology for ink and ink jet printing |
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| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
| US6297296B1 (en) | 1999-05-19 | 2001-10-02 | Kodak Polychrome Graphics Llc | Latex complexes as stabilized colorant |
| US6368395B1 (en) | 1999-05-24 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Subphthalocyanine colorants, ink compositions, and method of making the same |
| US6495660B2 (en) | 1999-10-20 | 2002-12-17 | Honeywell International Inc | Polyamide substrate |
| US6451887B1 (en) * | 2000-08-03 | 2002-09-17 | Ciba Specialty Chemicals Corporation | Benzotriazoles containing α-cumyl groups substituted by heteroatoms and compositions stabilized therewith |
| KR101157417B1 (en) * | 2004-10-28 | 2012-06-22 | 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 | Method of improving thermal stability |
| JP4693782B2 (en) * | 2004-11-19 | 2011-06-01 | キヤノン株式会社 | Inkjet recording medium and method for producing the same |
| JP5191739B2 (en) * | 2004-12-22 | 2013-05-08 | チバ ホールディング インコーポレーテッド | Anti-radical agent |
| WO2007122142A2 (en) * | 2006-04-24 | 2007-11-01 | Huntsman Advanced Materials (Switzerland) Gmbh | Process for the enhancement of thermostability |
| JP5675647B2 (en) | 2009-01-19 | 2015-02-25 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Organic black pigment and its production |
| JP6421132B2 (en) * | 2016-01-12 | 2018-11-07 | 大日精化工業株式会社 | Pigment dispersant, pigment composition, and pigment colorant |
| JP6532410B2 (en) * | 2016-01-12 | 2019-06-19 | 大日精化工業株式会社 | Pigment additive, pigment composition, and pigment colorant |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH13164A (en) * | 1896-11-04 | 1897-05-15 | Pierre Lormant | Hydro-lifting device |
| CH433296A (en) * | 1963-02-18 | 1967-04-15 | Ciba Geigy | Use of new hydroxyaryl-1,3,5-triazines as ultraviolet protection agents for non-textile organic materials |
| CH480402A (en) * | 1967-09-20 | 1969-10-31 | Geigy Ag J R | Process for stabilizing heat- and / or oxidation-sensitive non-textile materials |
| US4874391A (en) * | 1986-07-29 | 1989-10-17 | Ciba-Geigy Corporation | Process for photochemical stabilization of polyamide fiber material and mixtures thereof with other fibers: water-soluble copper complex dye and light-stabilizer |
| US4831068A (en) * | 1987-02-27 | 1989-05-16 | Ciba-Geigy Corporation | Process for improving the photochemical stability of dyeings on polyester fibre materials |
| ES2050274T3 (en) * | 1988-06-14 | 1994-05-16 | Ciba Geigy Ag | PROCEDURE FOR THE PHOTOCHEMICAL STABILIZATION OF UNDYED AND DYED POLYPROPYLENE FIBERS. |
| US5030243A (en) * | 1989-01-05 | 1991-07-09 | Ciba-Geigy Corporation | Process for the photochemical stabilization of undyed and dyeable artificial leather with a sterically hindered amine |
| EP0417040A1 (en) * | 1989-09-06 | 1991-03-13 | Ciba-Geigy Ag | Dyeing process for wool |
| US5069681A (en) * | 1990-01-03 | 1991-12-03 | Ciba-Geigy Corporation | Process for the photochemical stabilization of dyed polyamide fibres with foamed aqueous composition of copper organic complexes |
| DE59105066D1 (en) * | 1990-01-19 | 1995-05-11 | Ciba Geigy Ag | Stabilization of dyeings on polyamide fibers. |
-
1991
- 1991-05-22 DE DE59108599T patent/DE59108599D1/en not_active Expired - Fee Related
- 1991-05-22 EP EP91810388A patent/EP0459950B1/en not_active Expired - Lifetime
- 1991-05-24 US US07/705,429 patent/US5181935A/en not_active Expired - Fee Related
- 1991-05-29 CA CA002043484A patent/CA2043484A1/en not_active Abandoned
- 1991-05-31 JP JP3129155A patent/JP3051494B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3051494B2 (en) | 2000-06-12 |
| EP0459950A1 (en) | 1991-12-04 |
| DE59108599D1 (en) | 1997-04-17 |
| JPH04228678A (en) | 1992-08-18 |
| EP0459950B1 (en) | 1997-03-12 |
| US5181935A (en) | 1993-01-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |