EP2305786A1

EP2305786A1 - Process for cleaning or bleaching polyamide fabrics

Info

Publication number: EP2305786A1
Application number: EP09170857A
Authority: EP
Inventors: Hauke Rohwer; Menno Hazenkamp; Marie-Josée DUBS
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2009-09-21
Filing date: 2009-09-21
Publication date: 2011-04-06

Abstract

The instant invention relates to a bleaching process for polyamide or polyurethane/polyamide fibers and fabrics, which process is carried out in the presence of phthaloyl amido peroxy hexanoic acid (PAP) and selected fluorescent whitening agents.

Description

The instant invention relates to a bleaching process for polyamide or polyurethane/polyamide fibers and fabrics, which process is carried out in the presence of phthaloyl amido peroxy hexanoic acid (PAP) and selected fluorescent whitening agents.
Peroxide-containing bleaching agents have been used in washing and cleaning processes for some time. Typical examples are inorganic peroxides, such as, for example persulfates, perborates, percarbonates and/or persilicates. Organic peroxides are, for example, mono-peroxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperacetates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest.
In many cases fluorescent whitening agents are simultaneously applied. In the context of this invention, the term fluorescent whitening agent (FWA) is used as a synonym for optical brightener. Typical fluorescent whitening agents used in the context of a bleaching or laundering process are water soluble and from the chemical class of 4,4' bis sulfostyryl biphenyl or bis triazinyl stilbene sulfuric acid salts. Commercial examples are Tinopal CBS(RTM) and Tinopal DMA(RTM) from Ciba Inc.
When polyamide or polyurethane/polyamide (elastomeric) fibers or fabrics are treated in a washing or bleaching process containing phthaloyl amido peroxy hexanoic acid (PAP) and the above mentioned typical fluorescent whitening agents the effect of whitening is unsatisfying. The degree of whiteness is too low and the fibers or fabrics tend to receive a yellow shade.
It has now been found, that the whitening effect of specific fluorescent whitening agents is not reduced under bleach conditions in the presence of PAP.
One aspect of the invention is a washing or bleaching process for increasing the whiteness of polyamide or polyurethane/polyamide fibers or fabrics which process comprises bringing said fibers or fabrics in contact with a bleaching agent which is phthaloyl amido peroxy hexanoic acid and simultaneously with a fluorescent whitening agent which is selected from the group consisting of the stilbenyl-2H-naphthol (1,2-d) triazol derivatives, the bis(1,2,3-triazol-2yl) stilbene derivatives and the coumarine derivatives.
Polyamides are understood to be, for example, aliphatic and aromatic polyamides or copolyamides which are derived from diamines and dicarboxylic acids and/or of aminocarboxylic acid or the corresponding lactams. Suitable polyamides are for example: PA 6, PA 11, PA 12, PA 46, PA 66, PA 69, PA 610, PA 612, PA 10.12, PA 12.12 and also amorphous polyamides and polyurethane/polyamide elastomers. Polyamides and elastomers of the cited type are commonly known and are commercially available.
In one specific embodiment the fiber or fabric is a polyamide selected from the group consisting of PA 6, PA 11, PA 12, PA 46, PA 66, PA 69, PA 610, PA 612, PA 10.12, PA 12.12.
In another embodiment the fiber or fabric is a polyurethane/polyamide elastomer.
Fluorescent whitening agents from the classes of the stilbenyl-2H-naphthol (1,2-d) triazol derivatives, the bis(1,2,3-triazol-2yl) stilbene derivatives and the coumarine derivatives are known and for example described in Fluorescent Whitening Agents, Editor R. nliker, G. Müller, 1975, Georg Thieme Verlag Stuttgart, page 25 ff.
For example the fluorescent whitening agent is selected from the group consisting of

and
Compounds 101 to 107 are commercially available fluorescent whitening agents and, for example sold under the trade names Blankophor (RTM) from Bayer, Tinopal(RTM) or Uvitex(RTM) from Ciba Inc.
Preferably the fluorescent whitening agent is
or
For instance the amount of phthaloyl amido peroxy hexanoic acid is from 25-5000mg/kg fiber or fabric.
For example the amount of fluorescent whitening agent is from 5-500mg/kg fiber or fabric.
The instant washing or bleaching process is usually carried out in the presence of a nonionic and/or anionic surfactant.
Preferably the washing or bleaching process is carried out at a temperature between 15° C and 98° C.
The present invention relates to a washing or bleaching process.
Typically such a process is carried out in a mixture containing

I) 0 - 50 %, preferably 0 - 30 %, A) of an anionic surfactant and/or B) of a non-ionic surfactant,
II) 0 - 70 %, preferably 0 - 50 %, C) of a builder substance,
III) 0 - 10 %, preferably 0 - 5 % of phosphonates or aminoalkylene-poly(alkylenephosphonates),
IV) 0.5 - 99 %, preferably 0.5 - 50 %, D) of phthaloyl amido peroxy hexanoic acid, and 0.001 % to 0.1 % E) of a fluorescent whitening agent selected from the group consisting of the stilbenyl-2H-naphthol (1,2-d) triazol derivatives, the bis(1,2,3-triazol-2yl) stilbene derivatives and the coumarine derivatives

The above percentages are in each case percentage by weight, based on the total weight of the mixture.
When the mixture comprises a component A) and/or B), the amount thereof is preferably 1 - 50 %, especially 1 - 30 %.
When the mixture comprises phosphonates, carboxylates or aminoalkylene-poly(alkylenephosphonates or carboxylates), the amount thereof is preferably 1 - 3 %, especially 0.1 - 3 %.
When the mixture comprises a component C), the amount thereof is preferably 1 - 70 %, especially 1 - 50 %. Special preference is given to an amount of from 5 to 50 % and especially an amount of from 10 to 50 %.
Washing or bleaching processes are usually carried out by using an aqueous liquor.
The mixture can be, for example, a peroxide-containing complete washing agent or a separate bleaching agent. A bleaching agent is used for removing coloured stains on textiles in a separate liquor before the clothes are washed with a bleach-free washing agent. A bleaching additive can also be used in a liquor together with a bleach-free washing agent.
Granules can be prepared, for example, by first preparing an initial powder by spray-drying an aqueous suspension containing all the components listed above except for components D) and E), and then adding the dry components D) and E) and mixing everything together. It is also possible to add component E) to an aqueous suspension containing components A), B) and C), then to carry out spray-drying and then to mix component D) with the dry mass.
It is also possible to start with an aqueous suspension that contains components A) and C), but none or only some of component B). The suspension is spray-dried, then component E) is mixed with component B) and added, and then component D) is mixed in in the dry state.
It is also possible to mix all the components together in the dry state.
The anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxysulfates in which the alkyl radical has from 10 to 20 carbon atoms.
Preferred sulfonates are e.g. alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl radical. The cation in the case of anionic surfactants is preferably an alkali metal cation, especially sodium.
The anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkylsulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an a-sulfofatty acid salt or an ester thereof. Preferred are alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group, alkylsulfates having 8 to 18 carbon atoms, alkylethersulfates having 8 to 18 carbon atoms, and fatty acid salts being derived from palm oil or tallow and having 8 to 18 carbon atoms. The average molar number of ethylene oxide added in the alkylethersulfate is preferably 1 to 20, preferably 1 to 10. The salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium. Highly preferred carboxylates are alkali metal sarcosinates of formula R-CO(R₁)CH₂COOM₁ in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R₁ is C₁-C₄ alkyl and M₁ is an alkali metal, especially sodium.
The nonionic surfactant component may be, e.g., primary and secondary alcohol ethoxylates, especially the C₈-C₂₀ aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C₁₀-C₁₅ primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
The total amount of anionic surfactant and nonionic surfactant is preferably 5-50% by weight, preferably 5-40% by weight and more preferably 5-30% by weight. As to these surfactants it is preferred that the lower limit is 10% by weight.
Preferred carboxylates are alkali metal sarcosinates of formula R₁₉-CO-N(R₂₀)-CH₂COOM'¹ wherein R₁₉ is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl radical, R₂₀ is C₁-C₄alkyl and M'¹ is an alkali metal.
The non-ionic surfactant B) can be, for example, a condensation product of from 3 to 8 mol of ethylene oxide with 1 mol of a primary alcohol having from 9 to 15 carbon atoms.
As builder substance C) there come into consideration, for example, alkali metal phosphates, especially tripolyphosphates, carbonates or hydrogen carbonates, especially their sodium salts, silicates, aluminosilicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds. Especially suitable silicates are sodium salts of crystalline layered silicates of the formula NaHSi_tO_2t+1.pH₂O or Na₂Si_tO_2t+1.pH₂O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
Among the aluminosilicates, preference is given to those commercially available under the names zeolithe A, B, X and HS, and also to mixtures comprising two or more of those components. Zeolithe A is preferred.
Among the polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate either in racemic form or in the enantiomerically pure (S,S) form.
Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, hexamethylenediamin N,N,N',N' tetrakis methanphosphonic acid and diethylenetriaminepentamethylenephosphonic acid, as well as the salts therefrom.
The mixture may comprise, in addition to the combination according to the invention, one or more additional optical brighteners.
The detergent or bleach mixture used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; photobleaching agents; pigments; and/or shading agents. These constituents should, of course, be stable to any bleaching system employed. Such auxiliaries can be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10 % by weight, especially 0.5 to 5 % by weight, based on the total weight of the detergent.
Furthermore, the detergent or bleach mixture can optionally contain enzymes. Enzymes can be added to detergents for stain removal. The enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch. Examples of enzymes to be used include, but are by no means limited to, the following:

proteases as given in US-B-6,242,405 , column 14, lines 21 to 32;
lipases as given in US-B-6,242,405 , column 14, lines 33 to 46;
amylases as given in US-B-6,242,405 , column 14, lines 47 to 56; and
cellulases as given in US-B-6,242,405 , column 14, lines 57 to 64.

The enzymes can optionally be present in the detergent. When used, the enzymes are usually present in an amount of 0.01-5% by weight, preferably 0.05-5% and more preferably 0.1-4% by weight, based on the total weight of the detergent.
Also subject of the instant invention is the use of a fluorescent whitening agent which is selected from the group consisting of the stilbenyl-2H-naphthol (1,2-d) triazol derivatives, the bis(1,2,3-triazol-2yl) stilbene derivatives and the coumarine derivatives in a washing or bleaching process for increasing the whiteness of polyamide or polyurethane/polyamide fibers or fabrics wherein phthaloyl amido peroxy hexanoic acid is present as bleaching agent.
The definitions and preferences described above apply equally to all aspects of the invention.
The following examples illustrate the invention.

Application Examples

Washing is carried out in a LINITEST apparatus containing 45g bleached cotton, one sample of 5x5 cm of polyamide 6.6 without initial fluorescent whitening agent, (PA 6.6 w/o FWA), one sample of 5x5 cm of polyamide 6.6 containing an initial fluorescent whitening agent (PA 6.6 with FWA) and one sample of 5x5 cm polyamide / polyurethane 80/20 mixed fabric (PA/PUR).

Washing conditions:

Temperature:	30°C
Time:	45 Min
Washing Liquor:	1.176g ECE98 in 240ml tap water
PAP:	0.112g
pH:	9.0

Fluorescent whitening agents:

Comparative Example 1:	0.2% TINOPAL DMA-X
Comparative Example 2:	0.1% TINOPAL CBS-X
Example 3:	0.2% Compound 107
Example 4:	0.2% Compound 101

% is by weight and based on the weight of the detergent ECE 98

Results

For evaluating the degree of whiteness the lightness Y (according to CIE) is measured spectrophotometrically.

Table 1

Degree of Whiteness after 20 wash cycles
	PA 6.6 w/o FWA	PA 6.6 with FWA	PA/PUR
Initial Value	56	209	71
PAP without FWA	31	188	6
Comparative Example 1, 0.2% Tinopal DMA-X	45	187	31
Comparative Example 2, 0.1% Tinopal CBS	55	194	51
0.2% Example 3, compound 107	131	208	110
Example 4, 0.2% compound 101	137	208	145

The results clearly indicate a significant increase in whiteness for example 3 and 4, as compared to the comparative fluorescent whitening agents.

Claims

A washing or bleaching process for increasing the whiteness of polyamide or polyurethane/polyamide fibers or fabrics which process comprises bringing said fibers or fabrics in contact with a bleaching agent which is phthaloyl amido peroxy hexanoic acid and simultaneously with a fluorescent whitening agent which is selected from the group consisting of the stilbenyl-2H-naphthol (1,2-d) triazol derivatives, the bis(1,2,3-triazol-2yl) stilbene derivatives and the coumarine derivatives.
A washing or bleaching process according to claim 1 wherein the fiber or fabric is a polyamide selected from the group consisting of PA 6, PA 11, PA 12, PA 46, PA 66, PA 69, PA 610, PA 612, PA 10.12, PA 12.12
A washing or bleaching process according to claim 1 wherein the fiber or fabric is a polyurethane/polyamide elastomer.
A washing or bleaching process according to any of the preceding claims wherein the fluorescent whitening agent is selected from the group consisting of

and
A washing or bleaching process according to any of the preceding claims wherein the fluorescent whitening agent is
or
A washing or bleaching process according to any of the preceding claims wherein additionally a nonionic and/or anionic surfactant is present.
A washing or bleaching process according to any of the preceding claims wherein the amount of phthaloyl amido peroxy hexanoic acid is from25-5000mg/kg fiber or fabric.
A washing or bleaching process according to any of the preceding claims wherein the amount of fluorescent whitening agent is from 5-500mg/kg fiber or fabric.
A washing or bleaching process according to any of the preceding claims which process is carried out at a temperature between 15° C and 98° C.
Use of a fluorescent whitening agent which is selected from the group consisting of the stilbenyl-2H-naphthol (1,2-d) triazol derivatives, the bis(1,2,3-triazol-2yl) stilbene derivatives and the coumarine derivatives in a washing or bleaching process for increasing the whiteness of polyamide or polyurethane/polyamide fibers or fabrics wherein phthaloyl amido peroxy hexanoic acid is present as bleaching agent.