CA2051264A1 - Composition and process for the production of moulding-fast articles - Google Patents
Composition and process for the production of moulding-fast articlesInfo
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- CA2051264A1 CA2051264A1 CA002051264A CA2051264A CA2051264A1 CA 2051264 A1 CA2051264 A1 CA 2051264A1 CA 002051264 A CA002051264 A CA 002051264A CA 2051264 A CA2051264 A CA 2051264A CA 2051264 A1 CA2051264 A1 CA 2051264A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/614—Optical bleaching or brightening in aqueous solvents
Abstract
Composition and process for the production of moulding-fast articles Abstract of the disclosure Composition and process for the production of polyamide fibre-containing articles having improved moulding fastness properties using sterically hindered phenols.
Description
- 1 ~05~
Composition and process for the production of moulding-fast articles The present invention relates to a composition and a process for the production of polyamide fibre-containing, brilliant white or particularly bright-coloured articles having improved moulding fastness properties.
Certain articles made from synthetic fibres are shaped by thermal treatment (moulding).
These are, in particular, high-quality articles made from optically whitened polyamide fibres or those which comprise polyamide/polyurethane. The hot compression moulds generally cause a certain yellowing or even browning of the optically whitened textile material. This phenomenon is highly dependent on the polyamide quality, but in particular on the optical whitener, and results in variations in the product quality of articles of this type.
It has now been found that the use of certain hindered phenols and conventional optical whiteners also in combination with dyes, allows the above disadvantages to be entirely or at least substantially eliminated. Surprisingly, goods are obtained which, after moulding, have higher whileness, greater colour brightness and also lower quality variations compared with material which has only been optically whitened.
The invention therefore relates both to the use and a process using hindered phenols for improving the moulding fastness of polyamide fibre-containing material and to a composition for optically whitening polyamide fibre-containing articles which contains an optical whitener and a hindered phenol, and to a composition which also contains one or more dyes in addition to the hindered phenol and the optical whitener.
Hindered phenols in the context of the invention are compounds of the formula (I) (I) (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 formula (II) or (III)
Composition and process for the production of moulding-fast articles The present invention relates to a composition and a process for the production of polyamide fibre-containing, brilliant white or particularly bright-coloured articles having improved moulding fastness properties.
Certain articles made from synthetic fibres are shaped by thermal treatment (moulding).
These are, in particular, high-quality articles made from optically whitened polyamide fibres or those which comprise polyamide/polyurethane. The hot compression moulds generally cause a certain yellowing or even browning of the optically whitened textile material. This phenomenon is highly dependent on the polyamide quality, but in particular on the optical whitener, and results in variations in the product quality of articles of this type.
It has now been found that the use of certain hindered phenols and conventional optical whiteners also in combination with dyes, allows the above disadvantages to be entirely or at least substantially eliminated. Surprisingly, goods are obtained which, after moulding, have higher whileness, greater colour brightness and also lower quality variations compared with material which has only been optically whitened.
The invention therefore relates both to the use and a process using hindered phenols for improving the moulding fastness of polyamide fibre-containing material and to a composition for optically whitening polyamide fibre-containing articles which contains an optical whitener and a hindered phenol, and to a composition which also contains one or more dyes in addition to the hindered phenol and the optical whitener.
Hindered phenols in the context of the invention are compounds of the formula (I) (I) (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 formula (II) or (III)
- 2- 205~
(Il) ~ 1 2~ R3 (III) IR3 lOI~R~
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 or aryl group, and x, x' and y, independently of one another, are each 0 or 1, Z is an aliphatic or carbocyclic aromatic radical, the latter containing a maximum of two monocyclic or bicyclic rings, W is the sulfo group, and m and n, independently of one another, are 1 or 2, and water-soluble salts thereof.
In the formula (I), A is, for example, a monohydroxyphenyl radical in which at least one o-position to the hydroxyl group is substituted by an alkyl, cycloalkyl or araLkyl group and which also carries further substituents.
Alkyl groups in the o-position to the hydroxyl group of A may be straight-chain or branched and contain 1-12, preferably 4-8, carbon atoms. Preference is given here to a-branched alkyl groups. These are, for example, the methyl, ethyl, isopropyl, ten-butyl, isoamyl, octyl, tert-oc~yl and dodecyl groups. The tert-butyl group is particularly preferred.
Cycloalkyl groups in the o-pOSitiOIl to the hydroxyl group of A contain 6-10, preferably 6-8, carbon atoms. Examples are the cyclohexyl, methylcyclohexyl and cyclooctyl groups.
Aralkyl groups in the o-position to the hydroxyl group of A contain 7-10, preferably 8-9, carbon atoms. Examples are the a-metlhyl- and a,a-dimethylbenzyl groups.
The radical A may also be substituted by further alkyl, cycloalkyl or aralkyl groups as defined above, these preferably being in the o'- or p-position to the hydroxyl group so long as these positions are not occupied by the bond to Y. In addition, at least one m-position to the hydroxyl group is advantageously unsubstituted, while the other may be substituted by
(Il) ~ 1 2~ R3 (III) IR3 lOI~R~
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 or aryl group, and x, x' and y, independently of one another, are each 0 or 1, Z is an aliphatic or carbocyclic aromatic radical, the latter containing a maximum of two monocyclic or bicyclic rings, W is the sulfo group, and m and n, independently of one another, are 1 or 2, and water-soluble salts thereof.
In the formula (I), A is, for example, a monohydroxyphenyl radical in which at least one o-position to the hydroxyl group is substituted by an alkyl, cycloalkyl or araLkyl group and which also carries further substituents.
Alkyl groups in the o-position to the hydroxyl group of A may be straight-chain or branched and contain 1-12, preferably 4-8, carbon atoms. Preference is given here to a-branched alkyl groups. These are, for example, the methyl, ethyl, isopropyl, ten-butyl, isoamyl, octyl, tert-oc~yl and dodecyl groups. The tert-butyl group is particularly preferred.
Cycloalkyl groups in the o-pOSitiOIl to the hydroxyl group of A contain 6-10, preferably 6-8, carbon atoms. Examples are the cyclohexyl, methylcyclohexyl and cyclooctyl groups.
Aralkyl groups in the o-position to the hydroxyl group of A contain 7-10, preferably 8-9, carbon atoms. Examples are the a-metlhyl- and a,a-dimethylbenzyl groups.
The radical A may also be substituted by further alkyl, cycloalkyl or aralkyl groups as defined above, these preferably being in the o'- or p-position to the hydroxyl group so long as these positions are not occupied by the bond to Y. In addition, at least one m-position to the hydroxyl group is advantageously unsubstituted, while the other may be substituted by
3 2(~5~G~
a lower alkyl group, such as the methyl group.
For reasons of ready accessibility and their favourable action as moulding fastness improvers, particular preference is given to compounds of the formula (I) in which A is a radical of the formula (IV) R
(IV) H ~
in which R and Rl, independently of one another, are hydrogen, methyl or tert-butyl, and the total number of carbon atoms in R and R, is at least 2.
X and X' in the formulae (II) and (III) may be straight-chain or branched and contain 1 to 8, preferably 1 to 5, carbon atoms. Examples are the methylene, ethylene, trimethylene, propylene, 2-thiatrimethylene and 2-oxapentamethylene radicals.
Particular preference is given to compounds in which, in the radicals X and X', two hetero atoms are not bonded to the same saturated, i.e. tetrahedral, carbon atom.
An alkyl group R2 or R3 in the formulae (II) and (III) may be straight-chain or branched and may contain 1 lo 18, preferably 1 to 8, carbon atoms. Examples are the methyl, ethyl, isopropyl, pentyl, octyl, dodecyl and octadecyl groups.
A substituted alkyl group R2 or R3 is, for example, a hydroxyalkyl, alkoxyalkyl,aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl group having a total of 2 to 10, preferably 2 to 5, carbon atoms. Examples are the ~-hydroxyethyl"~-methoxyethyl,~-aminoethyl"~"B'-diethylaminoethyl and ,B-butylaminoethyl groups.
R2 or R3 may alternatively be an aryl group, preferably the phenyl group.
Compounds in which y in the formulae (II) and (III) is zero generally have a significantly better moulding fastness-improving action than those in which y is one.
a lower alkyl group, such as the methyl group.
For reasons of ready accessibility and their favourable action as moulding fastness improvers, particular preference is given to compounds of the formula (I) in which A is a radical of the formula (IV) R
(IV) H ~
in which R and Rl, independently of one another, are hydrogen, methyl or tert-butyl, and the total number of carbon atoms in R and R, is at least 2.
X and X' in the formulae (II) and (III) may be straight-chain or branched and contain 1 to 8, preferably 1 to 5, carbon atoms. Examples are the methylene, ethylene, trimethylene, propylene, 2-thiatrimethylene and 2-oxapentamethylene radicals.
Particular preference is given to compounds in which, in the radicals X and X', two hetero atoms are not bonded to the same saturated, i.e. tetrahedral, carbon atom.
An alkyl group R2 or R3 in the formulae (II) and (III) may be straight-chain or branched and may contain 1 lo 18, preferably 1 to 8, carbon atoms. Examples are the methyl, ethyl, isopropyl, pentyl, octyl, dodecyl and octadecyl groups.
A substituted alkyl group R2 or R3 is, for example, a hydroxyalkyl, alkoxyalkyl,aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl group having a total of 2 to 10, preferably 2 to 5, carbon atoms. Examples are the ~-hydroxyethyl"~-methoxyethyl,~-aminoethyl"~"B'-diethylaminoethyl and ,B-butylaminoethyl groups.
R2 or R3 may alternatively be an aryl group, preferably the phenyl group.
Compounds in which y in the formulae (II) and (III) is zero generally have a significantly better moulding fastness-improving action than those in which y is one.
- 4- 2~5~
Particular preference is given to compounds of the formula (I) in which Y is a radical of the formula (V) ~4 (V) -X"-C-N-in which R4 is hydrogen or Cl-C4alkyl, and X" is Cl-C4alkylene.
Z in the formula (I) is, for example, the radical of an unsubstituted or carboxyl-substituted lower aLkane having at least two carbon atoms, the radical of a benzene ring which is unsubstituted or substituted by chlorine, bromine, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4aLkoxycarbonylamino, hydroxyl, carboxyl, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino, it being possible for the group W to be bonded directly to this benzene ring or to a monocyclic aryl radical of one of its substituents, or is the naphthalene or tetralin radical.
A lower alkane radical Z may be straight-chain or branched and contain 2 to 5, preferably 2, carbon atoms. It is thus, for example, the ethylene, propylene, trimethylene or pentamethylene radical. This radical may also be substituted by carboxyl groups. An example in this case is the carboxyethylene radical.
A benzene radical Z in lhe formula (I) may also be further substituted. For example, it may contain straight-chain or branched, Cl-C4alkyl radicals, for example be substituted by methyl, ethyl or isopropyl groups; the methyl group is preferred here. Cl-C4Alkoxy groups as substituents of a benzene radical Z are, for example, the methoxy, ethoxy or butoxy groups. In a benzene radical Z which is substituted by an acylamino group, the acyl radical is derived, in particular, from a C2-C6aliphatic or monocarbocyclic aromatic carboxylic acid. Examples are the radicals of acetic, propionic"B-methoxypropionic, benzoic, aminobenzoic and methylbenzoic acids. Examples of Cl-C4alkoxycarbonylamino groups as substituents of a benzene radical Z are the methoxy-, ethoxy- and butoxycarbonylamino radicals.
If the group Z contains, as substituents, phenylethyl, styryl, phenyl, phenoxy, phenylthio or phenylsulfonyl groups, these may be substituted by chlorine, bromine, Cl-C4alkyl groups, such as the methyl group ,amino groups, Cl-C4alkoxy groups, such as Ihe methoxy group, acylamino groups, such as the acetyl- or benzoylamino group, or ~s~
- s -alkoxycarbonylamino groups, such as ~he methoxy- or ethoxycarbonylamino group.
It is also possible for a plurality of identical or different abovementioned substituents of the benzene radical Z or its aryl group-containing substituents to be present simultaneously.
A naphthalene radical Z may also be substituted by Cl-C4alkyl or alkoxy groups, such as the methyl or methoxy group.
The sulfo group W in the formula (I) is preferably free, but may also be in the form of its aLkali metal or alkaline earth metal salts, the ammonium salt or the salts of organic nitrogen bases whose cation conforms to the formula (VI) (VI) NR'R"R"'R""
in which R', R", R"', R"" are, independently of one another, hydrogen, a Cl-C4alkyl or ~-hydroxy-Cl-C4alkyl radical or a cyclohexyl radical, it being possible for at least two of these radicals to form a carbocyclic or heterocyclic ring system with one another.
Examples of organic nitrogen bases which are able to form such ammonium salts with the group W are trimethylamine, triethylamine, triethanolamine, diethanolamine, ethanolamine, cyclohexylamine, dicyclohexylamine, hexamethyleneimine and morpholinc.
Compounds which have a particularly favourable moulding fastness-improving action are those of the formula (VII) (VII) ~ X"- C - N~ Z--W
in which R and Rl, independently of one another, are methyl or tert-butyl, R4 is hydrogen or Cl-C4alkyl, X" is Cl-C4alkylene, Z is the ethylene radical, a divalent or trivalent radical ~512 of benzene or naphthalene or a divalent radical of diphenyl ether, W is the sulfo group and n is I or 2.
The group W in these compounds may be free or in the form of its salts as defined above.
Of the compounds of the formula (VII), those in which R = Rl = methyl are particularly advantageous economically, while those in which R = methyl and Rl = tert-butyl and in particular those in which R = Rl = tert-butyl have excellent alkali resistance.
The water-soluble compounds of the formula (I) are known, for example from US-A-3 665 031, and can be prepared by methods which are known per se.
Suitable compounds of the formula (I) which can be used according to the invention are, for example, compounds of the formula (VIII) R O R4 in which R, Rl, R4, X, Z, M and n are as defined below (Table 1).
7 205~L~~
Table 1:
pound R R, X R4 Z-SO3M M n 1 tertC4Hg tertC4Hg C2H4 H -CH2-CH2-SO3M Na 1 2 tertC4Hg tertC4H9 C2H4 H ~ S03M Na 1 3 tertC4Hg tertC4Hg C2H4 H ~ Na 1 M03S ~03M
4 tertC4Hg ~er~C4Hg C2H4 H ~ Na 1 ~ertC4H9 ~ertC4H9 C2H4 H ~ S03M Na 1 6 tertC4Hg ~er~C4Hg C2H4 H ~ Na 1 7 tertC4Hg ter~C4Hg C2H4 H M03S ~= ~ 0 ~3 Na 1 _ tenC4H9 tenCHg CzH4 H ~ ~3 SO3M Ntl - 8- 205~
Table 1: (continuation) pound R R, X R4 SO~M M n 9 tertC4Hg tertC4Hg C2H4 H ~ CH-2 CH~ ~sS
10 tertC4Hg tertC4Hg C2H4 H Cl~ O ~ Cl Na 11 tertC4Hg terlC4Hg C2H4 CH3 -CH2CH2-SO3M Na 12 2(tertC4Hg) 2(tertC4Hg) 2(C2H4 H ~ Na 2 13 tertC4Hg tertC4Hg C2H4 HMO3S ~0 ~CI Na 14 tertC4Hg tertC4Hg C2H4 H ~ Na CH,1 SO3M
15 tenC4Hg Lrr~CH~ CtH4 H o ~ SO3M Na 9 ~05~
Table 1: (continuation) pound R Rl X R4 Z-SO3M M n No. _ - SO3M _ 16 ter~C4H~tenC4H9C2H4 H ~ H= :H~3 a 17 tertC4Hg tertC4HgC2H4 H ~) Na 18 terlC4Hg tenC4HgCH2 H ~_ SO3M Na 19 ter~C4H9 tertC4HgC2H4C2H5 ~ SO3M Na 20 tertC4Hg tertC4HgC2H4 H ~ SO3M Na 21 ternC4Hg CH3 C2H4 H ~ SO3M Na 22 tertC4HgtenC4H9 C2H4 H--CH~3 SO3M Na - lo- ~O~G~
The compounds of the formula (I) are usually applied from an aqueous bath. The application can be carried out by an exhaust or continuous process before, during or after the optical whitening of the fibres. Application together with the optical whitener is preferred.
In the exhaust process, from 0.01 to 1 %, preferably from 0.05 to 0.5 %, of optical whitener and from 0.01 to 2 %, preferably from 0.05 to O.S %, of the compounds of the formula (I) can be employed.
In the continuous process, from 0.1 to 5 g/l, preferably from 0.2 to 2 g/l, of optical whitener and from 0.1 to 10 g/l, preferably from 0.2 to 2 g/l, of the compounds of the formula (I) can be employed.
Polyamide material is to be understood as meaning synthetic polyamide, for example nylon 6, nylon 6,6 or nylon 12 and modified polyamide, for example polyamide which can be dyed by means of basic dyes. In addition to pure polyamide fibres, blends of polyurethane and polyamide fibres are also particularly suitable, for example tricot material made from polyamide/polyurethane in the mixing ratio 70:30. In principle, the pure or mixed polyamide material can be present in a wide variety of processing forms, for example as fibres, yarn, woven fabric, knitted fabric, nonwoven fabric or pile material.
Examples of optical whiteners which are suitable for polyamide-containing materials are those of the general formulae (X) to (XVI).
Bistriazolylstilbenes of the general formula (X) (X) )~ N ~ CH--CH~ \NXF~
in which the radicals Rl, R2, R3 and R4 are, independently of one another, for example H, Cl-C6alkyl, phenyl or phenyl which is substituted, for example, by sulfonic acid groups, and their salts, for example alkali metal salts.
os~
Bistriazinylaminostilbenes of the general formula (XI) R~ R3 (XI) N ~ \ ~ NH ~ CH= CH ~ NH ~/ N
in which the radicals Rl, R2, R3 and R4 are, independcntly of one another, for example -HN ~ -HN ~ , -HN
N ~ O ,-N-(CI-C6hydroxyalkyl)2,-N-(Cl-C6alkyl)(Cl-C6hydroxyalkyl),-NH2, -N-(CI-C6alkyl)2, C~-C6alkoxy, Cl, -NH-(CI-C6alkylsulfonic acid) or -NH-(CI-C6hydroxyalkyl), and their salts, for example alkali metal salts.
Distyrylbiphenyls of the general formula (XII) (XII) ~ CH= CH ~ CH= CH ~ Rz in which the radicals Rl, R2, R3 and R4 are, independently of one another, for example H, sulfonyl or sulfinate, -SO2N(Cl-C6alkyl)2, -OCH3, -CN, -Cl, -COOCH3 or -CON(CI-C6alkyl)2, and their salts, for example alkali metal salts.
Bisbenzoxazolyl derivatives of the general formula (XIII) Z051;~
~0 0~
in which the radicals Rl, R2, R3 and R4 are, independently of one another, for example H, C1-C6alkyl, tert-butyl, ter~-butylphenyl or -COOCl-C6alkyl, and X is, for example CHe CH ~ CH= CH ~ , CH=CH- , ~ , or ~ .
Coumarins of the general formula (XIV) (XIV) ~0 2 in which Rl is, for example, H, Cl-C6alkyl or Cl-C6carboxylic acid, R2iS, for example, H, phenyl, carboxy-Cl-C6alkyl or --N~ J and R3 is, for exarnple, N
-HN ~ / ~ N N ~ N X
/N ~ CH3 N
- 13- 2(~5~
-O-(Cl-C6alkyl), -N(CI-C6alkyl)2 or -NH-CO-(CI-C6alkyl), and their salts, for example alkali metal salts.
Pyrazolines of the general formula (XV) (XV) ~r~
in which Rl is, for example, H, Cl or amine (including substituted amines), R2 is, for example, H, Cl, sulfonyl or sulfinate (including the derivatives, for example sulfonylamide), or carboxy-CI-C6alkyl, R3 and R4 are, independently of one another, for example H or Cl-C6alkyl, and R5 is, for example, H or Cl, and their salts, for exarnple alkali metal salts.
Dibenzofuranylbiphenyls of the general formula (XVI) (XVI) R2 ~ ~ C r ~ ~C ~ '~, R2 in which the radicals Rl, R2 and R3 are, independently of one another, for example H, halogen, CN, phenoxy, benzyloxy, Cl-C4alkyl, Cl-C4alkoxy or a sulfonic acid radical, and their salts, for example alkali metal salts.
The abovementioned whiteners are known and their preparation is described in a number of publications in the literature.
Suitable dyes for the process are all dyes which are suitable for dyeing the abovementioned textiles, such as azo, anthraquinone, nitro, acridone and naphthoquinone dyes.
A process for improving the moulding fastness of optically whitened textiles is claimed.
- 14 - 205~
The present invention furthermore relates to a composition for the optical whitening of polyamide rlbre-containing articles having improved moulding fastness properties. A
composition of this type, which can be applied from a bath, comprises a hindered phenol of the formula (I), an optical whitener for polyamide ~or a mixture thereof), one or more dyes in the case of coloured textiles, and, if desired, conventional assistants. Preferred compositions comprise a hindered phenol of the formula (I), particularly preferably of the formula (VII), and an optical whitener of the formulae (X)-(XV). The phenol:optical whitener ratio can be in the range from 100:1 to 1:50, a ratio of from 5:1 to 1:5 being preferred.
The composition for the optical whitening of polyamide fibre-containing articles having improved moulding faslness properties is prepared by mixing the components, including any assistants.
Examples of conventional assistants are dispersants, levelling agents and detergents, such as fatty alcohol polyglycol ethers, alkyl ethoxylates or alkylphenol ethoxylates, anionic alkylbenzenesulfonates or linear alkylsulfonates, alone or combined with benzimidazole derivatives or oxyethylated fatty amines, and sequestrants, such as the sodium salt of ethylenediaminetetraacetic acid, or bleaches, such as sodium dithionite, and combinations of two or more assistants.
The final shaping (moulding) of the textiles is carried out by customary methods.
The examples below illustrate the invention, but do not represent a limitation. In the following examples, parts and percentages are by weight, based on the weight of the textile, unless stated otherwise.
In the examples below, the textile used is a nylon 6 textured tricot. The whitener and the sterically hindered phenol are applied by the exhaust method, with 3 g/l of stabilised hydrosulfite (Clarit PS) additionally being added to the treatment bath. The treatment lasts 30 minutes at a temperature of 120~C.
The whiteness is determined by the Ganz method (Ganz, Appl. Optics 18, 1073-1078(1979)) using, a Zeiss RFC 3 spectrometer.
- 15- ~05~
Example 1: The compounds (4), (5), (7), (8) and (10) (see Table 1) are applied in conccntrations of 0.5 % in each case. The whiteness is from 70 to 80 units.
Example 2: The whitener of the formula Cl Cl ~ CH= CH{~ CH= CH~
SO3Na - SO3Na is applied in a concentration of 0.2 %. The whiteness is 270 units. Half of the textile piece is then subjected to the moulding test: in a "Rhodiaceta Thermotester" (Setaran, Lyon, France) with 13 heatable metal plates measuring 15x35 mm, the temperature of one of the central plates is set at 199C. The lower plinth is covered with a wool felt material about 3 mm thick. The textile piece is pressed for 1 minute (pressure about 70 g/cm2) and then its whiteness is measured again.
After the moulding test, the loss in whiteness is about 70 units.
Example 3: The whitener (concentration 0.2 %) from Example 2 and in each case one of thc compounds (4), (5), (7), (8), (10), (21) and (22) (see Table 1) (concentration 0.5 %) are applicd togelher. Each textile piece is subsequently subjected to the moulding test (199C, 1 minute).
The results are shown in Table 2 below.
Example 3a: The whitener (concentration 0.2 %) from Example 2 and the compound (23) in a concentration of 0.1 % are applied together. Each textile piece is subsequently subjected to the moulding test (199C, 1 minute).
Whiteness: 27 1 Loss in whiteness during moulding test: -24 Table 2:
_ ._ Loss in No . Compound White- whileness nesS during moulding test __ ._ tertC4Hg SO3H
(4) HO ~ CH2- CH2- C--NH~ 274 -31 tertC4Hg
Particular preference is given to compounds of the formula (I) in which Y is a radical of the formula (V) ~4 (V) -X"-C-N-in which R4 is hydrogen or Cl-C4alkyl, and X" is Cl-C4alkylene.
Z in the formula (I) is, for example, the radical of an unsubstituted or carboxyl-substituted lower aLkane having at least two carbon atoms, the radical of a benzene ring which is unsubstituted or substituted by chlorine, bromine, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4aLkoxycarbonylamino, hydroxyl, carboxyl, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino, it being possible for the group W to be bonded directly to this benzene ring or to a monocyclic aryl radical of one of its substituents, or is the naphthalene or tetralin radical.
A lower alkane radical Z may be straight-chain or branched and contain 2 to 5, preferably 2, carbon atoms. It is thus, for example, the ethylene, propylene, trimethylene or pentamethylene radical. This radical may also be substituted by carboxyl groups. An example in this case is the carboxyethylene radical.
A benzene radical Z in lhe formula (I) may also be further substituted. For example, it may contain straight-chain or branched, Cl-C4alkyl radicals, for example be substituted by methyl, ethyl or isopropyl groups; the methyl group is preferred here. Cl-C4Alkoxy groups as substituents of a benzene radical Z are, for example, the methoxy, ethoxy or butoxy groups. In a benzene radical Z which is substituted by an acylamino group, the acyl radical is derived, in particular, from a C2-C6aliphatic or monocarbocyclic aromatic carboxylic acid. Examples are the radicals of acetic, propionic"B-methoxypropionic, benzoic, aminobenzoic and methylbenzoic acids. Examples of Cl-C4alkoxycarbonylamino groups as substituents of a benzene radical Z are the methoxy-, ethoxy- and butoxycarbonylamino radicals.
If the group Z contains, as substituents, phenylethyl, styryl, phenyl, phenoxy, phenylthio or phenylsulfonyl groups, these may be substituted by chlorine, bromine, Cl-C4alkyl groups, such as the methyl group ,amino groups, Cl-C4alkoxy groups, such as Ihe methoxy group, acylamino groups, such as the acetyl- or benzoylamino group, or ~s~
- s -alkoxycarbonylamino groups, such as ~he methoxy- or ethoxycarbonylamino group.
It is also possible for a plurality of identical or different abovementioned substituents of the benzene radical Z or its aryl group-containing substituents to be present simultaneously.
A naphthalene radical Z may also be substituted by Cl-C4alkyl or alkoxy groups, such as the methyl or methoxy group.
The sulfo group W in the formula (I) is preferably free, but may also be in the form of its aLkali metal or alkaline earth metal salts, the ammonium salt or the salts of organic nitrogen bases whose cation conforms to the formula (VI) (VI) NR'R"R"'R""
in which R', R", R"', R"" are, independently of one another, hydrogen, a Cl-C4alkyl or ~-hydroxy-Cl-C4alkyl radical or a cyclohexyl radical, it being possible for at least two of these radicals to form a carbocyclic or heterocyclic ring system with one another.
Examples of organic nitrogen bases which are able to form such ammonium salts with the group W are trimethylamine, triethylamine, triethanolamine, diethanolamine, ethanolamine, cyclohexylamine, dicyclohexylamine, hexamethyleneimine and morpholinc.
Compounds which have a particularly favourable moulding fastness-improving action are those of the formula (VII) (VII) ~ X"- C - N~ Z--W
in which R and Rl, independently of one another, are methyl or tert-butyl, R4 is hydrogen or Cl-C4alkyl, X" is Cl-C4alkylene, Z is the ethylene radical, a divalent or trivalent radical ~512 of benzene or naphthalene or a divalent radical of diphenyl ether, W is the sulfo group and n is I or 2.
The group W in these compounds may be free or in the form of its salts as defined above.
Of the compounds of the formula (VII), those in which R = Rl = methyl are particularly advantageous economically, while those in which R = methyl and Rl = tert-butyl and in particular those in which R = Rl = tert-butyl have excellent alkali resistance.
The water-soluble compounds of the formula (I) are known, for example from US-A-3 665 031, and can be prepared by methods which are known per se.
Suitable compounds of the formula (I) which can be used according to the invention are, for example, compounds of the formula (VIII) R O R4 in which R, Rl, R4, X, Z, M and n are as defined below (Table 1).
7 205~L~~
Table 1:
pound R R, X R4 Z-SO3M M n 1 tertC4Hg tertC4Hg C2H4 H -CH2-CH2-SO3M Na 1 2 tertC4Hg tertC4H9 C2H4 H ~ S03M Na 1 3 tertC4Hg tertC4Hg C2H4 H ~ Na 1 M03S ~03M
4 tertC4Hg ~er~C4Hg C2H4 H ~ Na 1 ~ertC4H9 ~ertC4H9 C2H4 H ~ S03M Na 1 6 tertC4Hg ~er~C4Hg C2H4 H ~ Na 1 7 tertC4Hg ter~C4Hg C2H4 H M03S ~= ~ 0 ~3 Na 1 _ tenC4H9 tenCHg CzH4 H ~ ~3 SO3M Ntl - 8- 205~
Table 1: (continuation) pound R R, X R4 SO~M M n 9 tertC4Hg tertC4Hg C2H4 H ~ CH-2 CH~ ~sS
10 tertC4Hg tertC4Hg C2H4 H Cl~ O ~ Cl Na 11 tertC4Hg terlC4Hg C2H4 CH3 -CH2CH2-SO3M Na 12 2(tertC4Hg) 2(tertC4Hg) 2(C2H4 H ~ Na 2 13 tertC4Hg tertC4Hg C2H4 HMO3S ~0 ~CI Na 14 tertC4Hg tertC4Hg C2H4 H ~ Na CH,1 SO3M
15 tenC4Hg Lrr~CH~ CtH4 H o ~ SO3M Na 9 ~05~
Table 1: (continuation) pound R Rl X R4 Z-SO3M M n No. _ - SO3M _ 16 ter~C4H~tenC4H9C2H4 H ~ H= :H~3 a 17 tertC4Hg tertC4HgC2H4 H ~) Na 18 terlC4Hg tenC4HgCH2 H ~_ SO3M Na 19 ter~C4H9 tertC4HgC2H4C2H5 ~ SO3M Na 20 tertC4Hg tertC4HgC2H4 H ~ SO3M Na 21 ternC4Hg CH3 C2H4 H ~ SO3M Na 22 tertC4HgtenC4H9 C2H4 H--CH~3 SO3M Na - lo- ~O~G~
The compounds of the formula (I) are usually applied from an aqueous bath. The application can be carried out by an exhaust or continuous process before, during or after the optical whitening of the fibres. Application together with the optical whitener is preferred.
In the exhaust process, from 0.01 to 1 %, preferably from 0.05 to 0.5 %, of optical whitener and from 0.01 to 2 %, preferably from 0.05 to O.S %, of the compounds of the formula (I) can be employed.
In the continuous process, from 0.1 to 5 g/l, preferably from 0.2 to 2 g/l, of optical whitener and from 0.1 to 10 g/l, preferably from 0.2 to 2 g/l, of the compounds of the formula (I) can be employed.
Polyamide material is to be understood as meaning synthetic polyamide, for example nylon 6, nylon 6,6 or nylon 12 and modified polyamide, for example polyamide which can be dyed by means of basic dyes. In addition to pure polyamide fibres, blends of polyurethane and polyamide fibres are also particularly suitable, for example tricot material made from polyamide/polyurethane in the mixing ratio 70:30. In principle, the pure or mixed polyamide material can be present in a wide variety of processing forms, for example as fibres, yarn, woven fabric, knitted fabric, nonwoven fabric or pile material.
Examples of optical whiteners which are suitable for polyamide-containing materials are those of the general formulae (X) to (XVI).
Bistriazolylstilbenes of the general formula (X) (X) )~ N ~ CH--CH~ \NXF~
in which the radicals Rl, R2, R3 and R4 are, independently of one another, for example H, Cl-C6alkyl, phenyl or phenyl which is substituted, for example, by sulfonic acid groups, and their salts, for example alkali metal salts.
os~
Bistriazinylaminostilbenes of the general formula (XI) R~ R3 (XI) N ~ \ ~ NH ~ CH= CH ~ NH ~/ N
in which the radicals Rl, R2, R3 and R4 are, independcntly of one another, for example -HN ~ -HN ~ , -HN
N ~ O ,-N-(CI-C6hydroxyalkyl)2,-N-(Cl-C6alkyl)(Cl-C6hydroxyalkyl),-NH2, -N-(CI-C6alkyl)2, C~-C6alkoxy, Cl, -NH-(CI-C6alkylsulfonic acid) or -NH-(CI-C6hydroxyalkyl), and their salts, for example alkali metal salts.
Distyrylbiphenyls of the general formula (XII) (XII) ~ CH= CH ~ CH= CH ~ Rz in which the radicals Rl, R2, R3 and R4 are, independently of one another, for example H, sulfonyl or sulfinate, -SO2N(Cl-C6alkyl)2, -OCH3, -CN, -Cl, -COOCH3 or -CON(CI-C6alkyl)2, and their salts, for example alkali metal salts.
Bisbenzoxazolyl derivatives of the general formula (XIII) Z051;~
~0 0~
in which the radicals Rl, R2, R3 and R4 are, independently of one another, for example H, C1-C6alkyl, tert-butyl, ter~-butylphenyl or -COOCl-C6alkyl, and X is, for example CHe CH ~ CH= CH ~ , CH=CH- , ~ , or ~ .
Coumarins of the general formula (XIV) (XIV) ~0 2 in which Rl is, for example, H, Cl-C6alkyl or Cl-C6carboxylic acid, R2iS, for example, H, phenyl, carboxy-Cl-C6alkyl or --N~ J and R3 is, for exarnple, N
-HN ~ / ~ N N ~ N X
/N ~ CH3 N
- 13- 2(~5~
-O-(Cl-C6alkyl), -N(CI-C6alkyl)2 or -NH-CO-(CI-C6alkyl), and their salts, for example alkali metal salts.
Pyrazolines of the general formula (XV) (XV) ~r~
in which Rl is, for example, H, Cl or amine (including substituted amines), R2 is, for example, H, Cl, sulfonyl or sulfinate (including the derivatives, for example sulfonylamide), or carboxy-CI-C6alkyl, R3 and R4 are, independently of one another, for example H or Cl-C6alkyl, and R5 is, for example, H or Cl, and their salts, for exarnple alkali metal salts.
Dibenzofuranylbiphenyls of the general formula (XVI) (XVI) R2 ~ ~ C r ~ ~C ~ '~, R2 in which the radicals Rl, R2 and R3 are, independently of one another, for example H, halogen, CN, phenoxy, benzyloxy, Cl-C4alkyl, Cl-C4alkoxy or a sulfonic acid radical, and their salts, for example alkali metal salts.
The abovementioned whiteners are known and their preparation is described in a number of publications in the literature.
Suitable dyes for the process are all dyes which are suitable for dyeing the abovementioned textiles, such as azo, anthraquinone, nitro, acridone and naphthoquinone dyes.
A process for improving the moulding fastness of optically whitened textiles is claimed.
- 14 - 205~
The present invention furthermore relates to a composition for the optical whitening of polyamide rlbre-containing articles having improved moulding fastness properties. A
composition of this type, which can be applied from a bath, comprises a hindered phenol of the formula (I), an optical whitener for polyamide ~or a mixture thereof), one or more dyes in the case of coloured textiles, and, if desired, conventional assistants. Preferred compositions comprise a hindered phenol of the formula (I), particularly preferably of the formula (VII), and an optical whitener of the formulae (X)-(XV). The phenol:optical whitener ratio can be in the range from 100:1 to 1:50, a ratio of from 5:1 to 1:5 being preferred.
The composition for the optical whitening of polyamide fibre-containing articles having improved moulding faslness properties is prepared by mixing the components, including any assistants.
Examples of conventional assistants are dispersants, levelling agents and detergents, such as fatty alcohol polyglycol ethers, alkyl ethoxylates or alkylphenol ethoxylates, anionic alkylbenzenesulfonates or linear alkylsulfonates, alone or combined with benzimidazole derivatives or oxyethylated fatty amines, and sequestrants, such as the sodium salt of ethylenediaminetetraacetic acid, or bleaches, such as sodium dithionite, and combinations of two or more assistants.
The final shaping (moulding) of the textiles is carried out by customary methods.
The examples below illustrate the invention, but do not represent a limitation. In the following examples, parts and percentages are by weight, based on the weight of the textile, unless stated otherwise.
In the examples below, the textile used is a nylon 6 textured tricot. The whitener and the sterically hindered phenol are applied by the exhaust method, with 3 g/l of stabilised hydrosulfite (Clarit PS) additionally being added to the treatment bath. The treatment lasts 30 minutes at a temperature of 120~C.
The whiteness is determined by the Ganz method (Ganz, Appl. Optics 18, 1073-1078(1979)) using, a Zeiss RFC 3 spectrometer.
- 15- ~05~
Example 1: The compounds (4), (5), (7), (8) and (10) (see Table 1) are applied in conccntrations of 0.5 % in each case. The whiteness is from 70 to 80 units.
Example 2: The whitener of the formula Cl Cl ~ CH= CH{~ CH= CH~
SO3Na - SO3Na is applied in a concentration of 0.2 %. The whiteness is 270 units. Half of the textile piece is then subjected to the moulding test: in a "Rhodiaceta Thermotester" (Setaran, Lyon, France) with 13 heatable metal plates measuring 15x35 mm, the temperature of one of the central plates is set at 199C. The lower plinth is covered with a wool felt material about 3 mm thick. The textile piece is pressed for 1 minute (pressure about 70 g/cm2) and then its whiteness is measured again.
After the moulding test, the loss in whiteness is about 70 units.
Example 3: The whitener (concentration 0.2 %) from Example 2 and in each case one of thc compounds (4), (5), (7), (8), (10), (21) and (22) (see Table 1) (concentration 0.5 %) are applicd togelher. Each textile piece is subsequently subjected to the moulding test (199C, 1 minute).
The results are shown in Table 2 below.
Example 3a: The whitener (concentration 0.2 %) from Example 2 and the compound (23) in a concentration of 0.1 % are applied together. Each textile piece is subsequently subjected to the moulding test (199C, 1 minute).
Whiteness: 27 1 Loss in whiteness during moulding test: -24 Table 2:
_ ._ Loss in No . Compound White- whileness nesS during moulding test __ ._ tertC4Hg SO3H
(4) HO ~ CH2- CH2- C--NH~ 274 -31 tertC4Hg
(5) HO ~ CH2- CH2- C--NH~ SO3H 272 -29 tertC4Hg tertC4Hg SO3H
(7) HO ~ CH2- CH2- C--NH~ 265 -35 tertC4Hg O
tertC4H9 8) HO ~ CH2- CH2- C - NH~ O ~ SO3H 275 -19 terlC4Hg ~s~
Table 2: (continuation) _ Loss in No. Compound nWcshstL- dwhnteg ess moulding test tertCAHg Cl (10) H0 ~ CH2--CH2--C--NH~ 262 -32 tertC4Hg 0 tertC4Hg (21 ) H0 ~ CH2- CH2- C--NH~ S03H 273 -37 CH2 CH2- C -HN--CH2~ SO~H 272 -31 Similar results are achieved when the following compound is used:
Table 2: (continuation) _ Loss in No. Compound White- whiteness ness during . _ moulding test tertC4Hg (23) H0 ~HN - C ~ S03H 263 -19 tertC4Hg 205~2 Example 4: The whiteners of the formulae (A), (B), (C), (D) and (E) (see Table 3) in a concentration of 0.2 % are subjected to the moulding test (199C, I minute). In addition, in each case a whitener of the formula (A), (B), (C), (D) or (E) in a concentration of 0.2 %
and the compound (5) (see Table 1) tertC4Hg HO ~ CH2--CH2- C--NH~ SO3Na ter~C4Hg in a concentration of 0.5 % are applied together. Each textile piece is subsequently subjected to the moulding test (199C, 1 minute). The results are shown in Table 3 below.
~s~
c~=~
~E ~o ~ ~o ~ ~o ~
o ~ ~: o o o o . o o :~ ~
C~
~ Z ¢~ ~ O
2(~5 .
-c ~ CC o o . ~ o ; :~5~
Example 5: Two 20 g samples of a nylon 66 yard material are dyed at a liquor to goods ratio of 1:15 in a dyeing apparatus. The treatment baths contain 2 % of ammonium sulfate, 0.05 % of a nonionic surfactant (for example the product of the reaction of nonylphenol with 9.5 mol ethylene oxide), 0.3 % of the optical whitener of the formula (XX) SO3Na SO3Na (XX) ~ CH= CH~ CH= CH~
0.05 % of the pale violet dye of the formula (XXI) ~~ CH2NHCOCH2CI
(XXI) ~ CH3 C(CH3)3 H3C~CH3 rS03H
and 0.75 % of the hindered phenol of the formula (5).
The percentages in each case relate to the weight of the fibre material. The textile is treated therein for 10 minutes at 40C, then heated to 90C over the course of 20 minutes and dyed at this temperature for a further 10 minutes. 1 % of 80 % acetic acid is then added, the bath is cooled to 60C after 10 minutes, and the material is rinsed with cold water and dried. The textile fabric obtained in this way is dyed a pale violet colour and is subjected to the moulding test as described in Example 1. The comparison sample used is a textile fabric dyed by the same method, but with no added hindered phenol. The dye difference is then determined using D 65/10 light by the method of Cielar 1967/DIN 6174 (Table 4).
~(~5 Table 4:
Colori- with without metrichindered phenolhindered phenol quan_ities dL -().83 -1.38 da -2.05 -3.02 db 1.93 3.79 dc(ab) -2.54 -4.62 dH(ab) -1.22 -1.44 dE(ab) 2.94 5.04 Example 6: The dyeing liquor described in Example 5 contains 0.3 % of an opticalwhitener of the formula (XX), 0.02 % of the dye of the formula (XXI), 0.03 % of the dye of the formula (XXII) HO3S ~NH2 H2N ~ SO3H
OH N N OH
(XXII) N N
~'OS~3 0S~3 and 0.75 % of the sodium salt of the hindered phenol (9). A very bright pink dyeing is achieved.
The colour difference is evaluated as described in Example 5 and gives the following results (Table 5).
- 23 - 2~5~
Table 5:
Colori- with without metrichindered phenolhindered phenol quantities dL 0.34 -0.08 da -2.25 -3.18 db 1.60 2.54 dc(ab) -2.62 -3.91 dH(ab) -0.85 -1.16 dE(ab) 2.79 4.08
(7) HO ~ CH2- CH2- C--NH~ 265 -35 tertC4Hg O
tertC4H9 8) HO ~ CH2- CH2- C - NH~ O ~ SO3H 275 -19 terlC4Hg ~s~
Table 2: (continuation) _ Loss in No. Compound nWcshstL- dwhnteg ess moulding test tertCAHg Cl (10) H0 ~ CH2--CH2--C--NH~ 262 -32 tertC4Hg 0 tertC4Hg (21 ) H0 ~ CH2- CH2- C--NH~ S03H 273 -37 CH2 CH2- C -HN--CH2~ SO~H 272 -31 Similar results are achieved when the following compound is used:
Table 2: (continuation) _ Loss in No. Compound White- whiteness ness during . _ moulding test tertC4Hg (23) H0 ~HN - C ~ S03H 263 -19 tertC4Hg 205~2 Example 4: The whiteners of the formulae (A), (B), (C), (D) and (E) (see Table 3) in a concentration of 0.2 % are subjected to the moulding test (199C, I minute). In addition, in each case a whitener of the formula (A), (B), (C), (D) or (E) in a concentration of 0.2 %
and the compound (5) (see Table 1) tertC4Hg HO ~ CH2--CH2- C--NH~ SO3Na ter~C4Hg in a concentration of 0.5 % are applied together. Each textile piece is subsequently subjected to the moulding test (199C, 1 minute). The results are shown in Table 3 below.
~s~
c~=~
~E ~o ~ ~o ~ ~o ~
o ~ ~: o o o o . o o :~ ~
C~
~ Z ¢~ ~ O
2(~5 .
-c ~ CC o o . ~ o ; :~5~
Example 5: Two 20 g samples of a nylon 66 yard material are dyed at a liquor to goods ratio of 1:15 in a dyeing apparatus. The treatment baths contain 2 % of ammonium sulfate, 0.05 % of a nonionic surfactant (for example the product of the reaction of nonylphenol with 9.5 mol ethylene oxide), 0.3 % of the optical whitener of the formula (XX) SO3Na SO3Na (XX) ~ CH= CH~ CH= CH~
0.05 % of the pale violet dye of the formula (XXI) ~~ CH2NHCOCH2CI
(XXI) ~ CH3 C(CH3)3 H3C~CH3 rS03H
and 0.75 % of the hindered phenol of the formula (5).
The percentages in each case relate to the weight of the fibre material. The textile is treated therein for 10 minutes at 40C, then heated to 90C over the course of 20 minutes and dyed at this temperature for a further 10 minutes. 1 % of 80 % acetic acid is then added, the bath is cooled to 60C after 10 minutes, and the material is rinsed with cold water and dried. The textile fabric obtained in this way is dyed a pale violet colour and is subjected to the moulding test as described in Example 1. The comparison sample used is a textile fabric dyed by the same method, but with no added hindered phenol. The dye difference is then determined using D 65/10 light by the method of Cielar 1967/DIN 6174 (Table 4).
~(~5 Table 4:
Colori- with without metrichindered phenolhindered phenol quan_ities dL -().83 -1.38 da -2.05 -3.02 db 1.93 3.79 dc(ab) -2.54 -4.62 dH(ab) -1.22 -1.44 dE(ab) 2.94 5.04 Example 6: The dyeing liquor described in Example 5 contains 0.3 % of an opticalwhitener of the formula (XX), 0.02 % of the dye of the formula (XXI), 0.03 % of the dye of the formula (XXII) HO3S ~NH2 H2N ~ SO3H
OH N N OH
(XXII) N N
~'OS~3 0S~3 and 0.75 % of the sodium salt of the hindered phenol (9). A very bright pink dyeing is achieved.
The colour difference is evaluated as described in Example 5 and gives the following results (Table 5).
- 23 - 2~5~
Table 5:
Colori- with without metrichindered phenolhindered phenol quantities dL 0.34 -0.08 da -2.25 -3.18 db 1.60 2.54 dc(ab) -2.62 -3.91 dH(ab) -0.85 -1.16 dE(ab) 2.79 4.08
Claims (26)
1. A process for the production of polyamide fibre-containing articles having improved moulding fastness properties, which comprises applying a compound of the formula (I) (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 formula (II) or (III) (II) (III) 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 or aryl group, and x, x' and y, independently of one another, are each 0 or 1, Z is an aliphatic or carbocyclic aromatic radical, the latter containing a maximum of two monocyclic or bicyclic rings, W is the sulfo group, and m and n, independently of one another, are 1 or 2, or a water-soluble salt thereof, to the fibres before, during or after the optical whitening and, if appropriate, dyeing of the fibres.
2. A process according to claim 1, wherein a compound of the formula (I) is used in which A is a monohydroxyphenyl radical in which at least one o-position to the hydroxyl group is substituted by alkyl having 1-12 carbon atoms, cycloalkyl having 6-10 carbon atoms or aralkyl having 7-10 carbon atoms, and which may also carry further substituents.
3. A process according to either of claims 1 and 2, wherein a compound of the formula (I) is used in which A is a radical of the formula (IV) (IV) in which R and R1, independently of one another, are hydrogen, methyl or tert-butyl, and the total number of carbon atoms in R and R1 is at least 2.
4. A process according to any one of claims 1 to 3, in which X and X' in the compounds of the formulae (II) and (III) are straight-chain or branched alkylene having 1-8 carbon atoms.
5. A process according to any one of claims 1 to 4, in which R2 and R3 in the compounds of the formulae (II) and (III) are straight-chain or branched C1-C8alkyl.
6. A process according to either of claims 1 and 4, in which R2 and R3 in the compounds of the formulae (II) and (III) are hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl, in each case having a total of 2-10 carbon atoms, or phenyl.
7. A process according to claim 1, in which Y in the formula (I) is a radical of the formula (V) (V) 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 the formula (I) is the radical of an unsubstituted or carboxyl-substituted alkane having at least 2 carbon atoms, the radical of a benzene ring which is unsubstituted or substituted by chlorine, bromine, C1-C4alkyl, C1-C4alkoxy, C1-C4alkoxycarbonylamino, hydroxyl, carboxyl, phenylethyl, styryl, phenyl, phenoxy, phenylthio, phenylsulfonyl or acylamino, it being possible for the group W to be bonded directly to this benzene ring or to a monocyclic aryl radical of one of its substituents, or is the naphthalene or tetralin radical.
9. A process according to claim 1, wherein a compound of the formula (VII) (VII) in which R and R1, independently of one another, arç methyl or tert-butyl, R4 is hydrogen or C1-C4alkyl, X" is C1-C4alkylene, Z is the ethylene radical, a divalent or trivalent radical of benzene or naphthalene, or a divalent radical of diphenyl ether, W is the sulfo group and n is 1 or 2, is used.
10. A process according to claim 9, wherein a compound of the formula (VII) is used in which R and R1 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 one of the radicals or , in which the sulfo group W is in the form of its alkali metal or ammomum salt.
11. A process according to any one of claims 1-10, wherein the optical whitener used is a whitener having the basic structure of a bistriazinylaminostilbene, bistriazolylstilbene, distyrylbiphenyl, bisbenzoxazolyl derivative, coumarin or pyrazoline.
12. A process according to claim 11, wherein a mixture of an optical whitener and one or more dyes, such as azo, anthraquinone, nitro, acridone or naphthoquinone dyes, is used.
13. A process according to any one of claims 1-12, wherein a compound of the formula (I) in a concentration of from 0.01 to 2 % in the case of the exhaust process or in an amount of from 0.1 to 10 g/l in the case of the conlinuous process, is used.
14. A process according to claim 13, wherein a compound of the formula (1) is used in a concentration of from 0.05 to 0.5 % in the case of the exhaust process or in an amount of from 0.2 to 2 g/l in thc case of the continuous process.
15. A polyamide fibre-containing article having improved moulding fastness properties which has been treated by a process according to claim 1.
16. A composition comprising a hindered phenol of the formula (I) (I) (A-Y-)nZ(-w)m in which A is thc radical of a sterically hindered phenol from the benzene series, Y is a radical of thc formula (II) or (III) (II) (III) 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 carbocyclic aromatic radical, the latter containing a maximum of two monocyclic or bicyclic rings, W is the sulfo group, and m and n, independently of one another, are 1 or 2, or a water-soluble salt thereof, an optical whitener for polyamide, or a mixture thereof, and, if desired, a dye or a dye mixture.
is an aliphatic or carbocyclic aromatic radical, the latter containing a maximum of two monocyclic or bicyclic rings, W is the sulfo group, and m and n, independently of one another, are 1 or 2, or a water-soluble salt thereof, an optical whitener for polyamide, or a mixture thereof, and, if desired, a dye or a dye mixture.
17. A composition according to claim 16, wherein the hindered phenol is a compound of the formula (VII) (VII) 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 the ethylene radical, a divalent or trivalent radical of benzene or naphthalene, or a divalent radical of diphenyl ether, W is the sulfo group, and n is 1 or2.
18. A composition according to claim 17, wherein the optical whitener has the basic structure of a bistriazinylaminostilbene, bistriazolylstilbene, distyrylbiphenyl, bisbenzoxazolyl derivative, coumarin, pyrazoline or dibenzofuranylbiphenyl.
19. A composition according to claim 18, which contains a dye or a mixture of dyes from the group comprising the azo and anthraquinone dyes.
20. A composition according to claim 19, wherein the hindered phenol:optical whitener ratio is in the range from 100:1 to 1:50.
21. A composition according to claim 20, wherein the hindered phenol:optical whitener ratio is in the range from 5:1 to 1:5.
22. A composition according to claim 21, wherein lhe hindered phenol:dye or dye mixture ratio is in the range from 50:1 to 1:50.
23. A composition according to claim 21, wherein the hindered phenol is a compound of the formula (VII) (VII) 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 the ethylene radical, a divalent or trivalent radical of benzene or naphthalene, or a divalent radical of diphenyl ether, W is the sulfo group, and n is 1 or 2, and the optical whitener has the basic structure of a distyrylbiphenyl.
24. A composition according to claim 23, which contains an azo dye or an anthraquinone dye or a mixture thereof.
25. A process for the preparation of a composition according to claim 16, wherein the components are mixed, if desired with addition of assistants.
26. A process according to claim 1 for improving the moulding fastness of optically whitened textiles.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2988/90-5 | 1990-09-14 | ||
| CH298890 | 1990-09-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2051264A1 true CA2051264A1 (en) | 1992-03-15 |
Family
ID=4246136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002051264A Abandoned CA2051264A1 (en) | 1990-09-14 | 1991-09-12 | Composition and process for the production of moulding-fast articles |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0475907B1 (en) |
| JP (1) | JP3296833B2 (en) |
| CA (1) | CA2051264A1 (en) |
| DE (1) | DE59106812D1 (en) |
| ES (1) | ES2079055T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0621266A1 (en) * | 1993-04-22 | 1994-10-26 | Ciba-Geigy Ag | Sterically hindered phenols and their use for the stabilisation of polyamide fibres |
| 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 |
| CN1325878A (en) * | 2000-05-26 | 2001-12-12 | 上海博德基因开发有限公司 | Polypeptide-human interferon alpha receptor 115.62 and polynucleotide for coding it |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD51983A (en) * | ||||
| GB1118876A (en) * | 1964-08-04 | 1968-07-03 | Ici Ltd | Improvements in the treatment of synthetic polyester shaped articles |
| CH480402A (en) * | 1967-09-20 | 1969-10-31 | Geigy Ag J R | Process for stabilizing heat- and / or oxidation-sensitive non-textile materials |
| US3940410A (en) * | 1973-09-11 | 1976-02-24 | Sandoz Ltd., (Sandoz Ag) | Bis-benzonazoledicarbonitriles |
| JPS5851972B2 (en) * | 1976-05-14 | 1983-11-19 | 昭和化学工業株式会社 | 1,4-bis-styrylbenzene derivative and its production method |
| CH677167B5 (en) * | 1985-05-08 | 1991-10-31 | Sandoz Ag |
-
1991
- 1991-09-05 DE DE59106812T patent/DE59106812D1/en not_active Expired - Fee Related
- 1991-09-05 EP EP91810712A patent/EP0475907B1/en not_active Expired - Lifetime
- 1991-09-05 ES ES91810712T patent/ES2079055T3/en not_active Expired - Lifetime
- 1991-09-12 CA CA002051264A patent/CA2051264A1/en not_active Abandoned
- 1991-09-13 JP JP23482291A patent/JP3296833B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3296833B2 (en) | 2002-07-02 |
| ES2079055T3 (en) | 1996-01-01 |
| DE59106812D1 (en) | 1995-12-07 |
| EP0475907B1 (en) | 1995-11-02 |
| EP0475907A3 (en) | 1992-04-22 |
| EP0475907A2 (en) | 1992-03-18 |
| JPH04272282A (en) | 1992-09-29 |
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| EEER | Examination request | ||
| FZDE | Dead |