JP2003520907A - How to bleach woven or knitted fabric - Google Patents

Abstract

  (57) [Summary] According to the present invention, there is provided a method for cleaning a woven or knitted fabric using a bleaching agent composition and a detergent composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a method of bleaching a woven or knitted fabric with a bleach composition containing a peroxycarboxylic acid.

[0002]

[Prior art]

Detergent compositions suitable for laundry applications are well known in the art. Detergent compositions that rely on hypochlorite as a bleaching agent are preferred over oxygen bleaching agents primarily for performance, especially at low temperatures. Normally, the oxygen bleach used is
An oxygen bleach precursor perborate or percarboxylic acid that reacts with active species to produce hydrogen peroxide.

However, the convenience of hypochlorite bleaches has some limitations. In particular, it is well known to consumers that hypochlorite bleaches can cause yellowing and / or damage to bleached woven and knitted fabrics. This is especially true for synthetic woven and knitted fabrics, and there is a fixed prejudice against the use of hypochlorite bleach in synthetic fibers, as can be seen from the warnings on the commercial hypochlorite bleach label. Also, various woven and knitted fabrics made from or containing synthetic fibers have been labeled by the manufacturer as non-bleachable.

Manufacturers are therefore faced with achieving a balance between cleaning performance and woven and / or knit and / or color damage. The inventor has found that a peroxycarboxylic acid bleach, which is a weaker bleaching agent than hypochlorite, provides improved cleaning in all formulated detergent compositions as compared to the currently most used oxygen bleaching precursors. It has been found to provide performance. Peroxycarboxylic acid bleaches are known in the art, for example EP 435,37.
Known as No. 9.

However, despite the apparent compatibility of this bleaching agent, it has occasionally been found that cleaning performance does not meet consumer expectations well.

[0006]

[Problems to be Solved by the Invention]

It is therefore an object of the present invention to address the above mentioned problems, namely to provide improved overall stain removal performance against a wide range of stains in addition to color and woven and knit safety. is there. It has been found that these problems are effectively addressed when cleaning woven and knitted fabrics using certain woven and knitted bleaching methods. It has also been found that when a woven or knitted fabric is treated using the method of the present invention, the woven or knitted fabric has improved bleaching performance as well as improved overall stain removal performance. Also surprisingly, by using the woven and knitted bleaching method of the present invention, improved greasy stain removal and especially as compared to conventional all-prescription detergent compositions containing the same bleaching agent. It has been found that enzymatic stain removal can be achieved. It has further been found that damage to woven and / or knit and / or color can be minimized using the methods described herein. Applicants therefore believe that they have achieved a balance of cleaning performance and damage to the woven / knit / color.

[0007]

[Means for Solving the Problems]

The present invention is a method of cleaning a woven or knitted fabric with a bleaching composition and a detergent composition comprising the following discrete steps: (a) contacting the woven or knitted fabric with a bleaching composition containing a preformed peroxycarboxylic acid. And (b) contacting the woven or knitted fabric with a detergent composition, and (c) rinsing the woven or knitted fabric with water.

DETAILED DESCRIPTION OF THE INVENTION The present invention includes the method of bleaching woven and knitted fabrics described below. "Woven and knitted fabric" means any type of woven fabric, including natural and synthetic woven and knitted fabrics, used for making clothes, curtains, drapes, bed linens, bath linens, tablecloths, sleeping bags, tents, covered furniture, etc. It is understood as a knit. "Natural" woven or knitted fabrics are those made from cotton, viscose, flax, silk and / or wood. "
“Synthetic” woven and knitted fabrics are made from synthetic fibers such as polymeric fibers (polyamide, polyester, Lycra® and elasthane®), as well as from both natural and synthetic fibers. is there.

Method The method of the present invention comprises contacting the woven or knitted fabric with the bleaching composition in the first stage (a) and contacting the woven or knitted fabric with the detergent composition in the independent second stage (b). The first step may be performed before the second step, or the second step may be performed before the first step.

While each step of the method may be performed manually, in a preferred embodiment of the invention the method is performed in a washing machine having at least one rinse cycle and wash cycle. Generally, washing machines have a pre-rinse cycle in which the woven or knitted fabric is at least moistened with water.
This preliminary rinse cycle may be followed by additional rinse cycles, but usually with a main wash cycle. The detergent composition is conventionally supplied in the main wash cycle. The main wash cycle is followed by at least one post-wash cycle, preferably at least two rinse cycles. Step (a) is preferably carried out in a preliminary rinse and / or at least one post-wash cycle. It is preferred to perform step (b) in the main wash cycle.

In the method of bleaching a woven or knitted fabric of the present invention, the bleaching agent composition is contacted with the woven or knitted fabric for a time sufficient to bleach the woven or knitted fabric. When used in diluted form, the acidic aqueous liquid composition is contacted with the woven or knitted fabric for up to 24 hours, preferably 1 minute to 12 hours, more preferably 20 minutes to 6 hours. When used as is, the acidic aqueous liquid composition is woven and knitted for up to 24 hours, preferably 1 minute to 2 minutes.
The contact is performed for a time, more preferably for 1 minute to 1 hour.

The temperature of the bleaching process affects the stain removal and / or bleaching performance of the bleach composition. More specifically, increasing the temperature accelerates the bleaching process, i.e. reduces the time required to bleach a given soil. When the bleach composition described herein is used diluted, step (a) of the bleaching process of the present invention comprises 4 to 60 ° C, preferably 10 to 50 ° C, most preferably 20 to 40 ° C. Is preferably performed.

The method for bleaching a woven or knitted fabric of the present invention further includes, as an essential step, rinsing the woven or knitted fabric with water after contacting the bleaching agent composition and the detergent composition. This can be done manually in a water container, by placing the woven or knitted fabric in flowing water, or by a washing machine rinse cycle.

Indeed, although one, two or all three steps of the method of the invention may be carried out manually, for the convenience of the user, at least one, more preferably two, and most preferably all steps may be carried out in a washing machine. preferable.

Bleach Composition The method of the present invention requires contacting the woven or knitted fabric with a bleach composition containing a preformed peroxycarboxylic acid (hereinafter referred to as a peracid). In a preferred embodiment of the present invention, the peracid has the general formula

[Chemical 3] Have.

Wherein R is a linear or branched alkyl chain having at least 1 carbon atom, X is alkyl, especially an alkyl chain of 1 to 24 carbon atoms, aryl,
Halogen, ester, ether, amine, amide, substituted amino phthalate, imide, hydroxide, sulfide, sulfate, sulfonate, carboxylic acids, heterocyclics, nitrate, aldehyde, phosphonate, phosphonic acids or mixtures thereof It is a substituent or hydrogen atom selected from the group.

More specifically, the R group preferably contains from 2 to 24 carbon atoms. Further, the R group is aryl, halogen, ester, ether, amine, amide, substituted amino phthalate, imide, hydroxide, sulfide, sulfate, sulfonate, carboxylic acid, heterocyclic group, nitrate, aldehyde, ketone, or those. A branched alkyl chain containing one or more side chains containing a substituent selected from the group consisting of a mixture of

The X group in the preferred peracids of the above general formula is a phthalimido group. Therefore, a particularly preferred peracid has the general formula:

[Chemical 4] Is to have.

Wherein R is a C _1-20 alkyl group and A, B, C and D are independently alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxyl, sulfate, sulfonate, aldehyde Or a substituent or a hydrogen atom individually selected from the group consisting of a mixture thereof.

In a preferred aspect of the invention R is an alkyl group having 3 to 12, more preferably 5 to 9 carbon atoms. Preferred substituents A, B, C and D are linear or branched alkyl groups having 1 to 5 carbon atoms, more preferably hydrogen atoms.

Preferred peracids are phthaloylamide peroxyhexanoic acid (also known as phthaloylamide-peroxycaproic acid), phthaloylamide peroxyheptanoic acid, phthaloylamide peroxyoctanoic acid, phthaloylamide peroxynonanoic acid, phthaloylamide. It is selected from the group consisting of peroxydecanoic acid and mixtures thereof.

[0022]   An even more preferred peracid has the general formula:

[Chemical 5] (Wherein R is selected from C _1-4 alkyl groups and n is an integer of 1 to 5).

In one particularly preferred aspect of the present invention, the peracid is where R is CH ₂ and n is 5, ie phthaloylamido-peroxycaproic acid, ie PAP. The peracid is preferably used as a substantially water insoluble solid or wet cake and is commercially available from Ausimont under the tradename Euroco. The peracid may be present in the composition at a concentration of 0.1-10%, more preferably 0.5-8%, most preferably 1-6%. Also, the peracid is of very high concentration, eg 1
It may be present at 0-40%, more preferably 15-30%, most preferably 20-25%.

The bleaching composition may be in a granular form, but is preferably in a liquid form. The term liquid is understood to include gels or pastes. When the bleach composition is a liquid, preferably 10 to 99% by weight of the bleach composition, more preferably 5
It is preferably aqueous containing water in a concentration of 0 to 98% by weight. The bleach composition may contain other components in addition to the peracid. Examples of such ingredients are provided herein as optional ingredients. Preferred optional ingredients include surfactants, preferably anionic surfactants. It is also particularly preferred in this embodiment that the surfactant be present at a concentration of less than 5%.

Another particularly preferred ingredient is a suspending agent. Suspending agents are components that aid or facilitate the suspension of insoluble or partially insoluble solids in a liquid environment. Currently available peracids are generally solid and substantially water insoluble. When the solid particles are placed in a liquid composition, the particles fall to the bottom of the container containing the liquid. A method of homogeneously distributing a solid (eg, a peracid) in a liquid composition is to include a suspending agent. In the present invention, preferred suspending agents are polymers such as natural gum polymers (eg xanthan gum), crosslinked polycarboxylic acids, polyvinyl polymers (PVA, PVP, etc.). Preferably the suspending agent of the present invention is selected from xanthan gum, crosslinked polycarboxylic acids and mixtures thereof.

The bleaching composition is preferably acidic, ie the bleaching composition preferably has a pH value of less than 7, more preferably 1 to 8.5, most preferably 3 to 4.

Here, the “diluted form” means that the composition described below is diluted by a user, preferably with water. Such dilution occurs, for example, by hand washing as well as other methods such as washing machines. The composition is up to 500 times, preferably 5
It can be diluted 200 to 200 times, more preferably 10 to 80 times. In a preferred embodiment of the invention the composition is used in diluted form.

An advantage of the bleaching compositions suitable for use in the woven and knitting bleaching method of the invention is that they are physically and chemically stable during storage. The chemical stability of these compositions can be evaluated by measuring the effective oxygen concentration for a given storage period after the composition has been manufactured. The term “chemically stable” as used herein means that the composition used in the present invention does not undergo a loss of more than 15% AvO at 25 ° C. for one month, preferably a loss of 10% or less of peracid. It means to contain.

The available oxygen (AvO) loss of the peracid-containing composition can be measured by reducing with a solution containing ferrous ammonium sulfate and then titrating with potassium permanganate. The stability test is well known to the person skilled in the art, for example Cur available from Interox.
It is reported in the technical information sheet of ox (registered trademark). Further, the peracid concentration can be determined by referring to the literature on peracid (F, Difuria et al., Gas-liquid chromatography method for measuring peracid, Analyst, Volume 113, May 1988, pp. 793-795 (F. Di Fu
ria et al., Gas-liquid Chromatography Method for Determination of Peracid
, Analyst, Vol 113, May 1988, p793-795)). Here, "physically stable" means 5 in the bleaching composition used in the present invention.
This means that no phase separation occurs at 0 ° C for 7 days.

Detergent Composition The method of the present invention involves contacting the woven or knitted fabric with the detergent composition. The term detergent composition is understood to be all prescription detergent compositions currently on the market. These compositions are generally expected to be used in the washing cycle of washing machines. The detergent composition contains conventional detergent ingredients. Conventional detergent ingredients suitable for use in such detergent compositions include, for example, co-pending patent applications UK 96 / 16112.0, UK 97 / 139466.3, or WO 96/28531 or EP-B-. No. 707626.

Such liquid detergent and / or granular detergent compositions are also preferably builders (up to 80%), organic polymeric compounds (up to 20%), bleaches (up to 25%), bleach activators. (Up to 15%), enzyme (usually 0.0001-2%), antifoam (4
%), Dispersant (up to 15%), lime soap dispersant (up to 15%), soil suspension agent (up to 20%), anti-redeposition agent (up to 20%), corrosion inhibitor (up to 10%) , A solvent (up to 20%), a chelating agent (up to 15%), a dye, a pigment, a perfume, and the like, and at least one other conventional detergent component may be contained. The exact nature of the additional conventional detergent ingredients and their added concentrations will depend on the physical form of the detergent composition and the desired properties of the composition.

The detergent composition of the present invention contains other mild bleaching agents or bleaching systems, such as bleach precursors and bleach activators, but no peracids. The detergent composition is in the form of granules or liquid. Preferably the detergent composition comprises a surfactant, the concentration of said surfactant being above 5%.

When the detergent composition is liquid or granular, the pH of the 1% solution is 7
It is larger, more preferably larger than 9, and most preferably in the range 9 to 11.5. The pH of both the bleach composition and the detergent composition may be adjusted using any acidic or alkaline agent known to those skilled in the art. Examples of acidifying agents are organic acids such as citric acid, inorganic acids such as sulfuric acid, sulphonic acid and / or methanesulphonic acid. Examples of alkaline agents are sodium hydroxide, potassium hydroxide and / or sodium carbonate. Generally, such liquid detergent compositions and / or granular detergent compositions are diluted with 250 times their weight in water, preferably 2-200 times, more preferably 10-160 times, and are described herein. To obtain an alkaline solution. Such dilution occurs in other ways, for example by hand washing as well as washing machines.

Optional Ingredients The bleaching composition used in the method for bleaching woven and knitted fabrics of the present invention further comprises a surfactant, a chelating agent, a radical scavenger, an antioxidant, a stabilizer, a builder, a soil suspending agent and a polymeric soil. Release agent, dye transfer agent, solvent, antifoaming agent, whitening agent, fragrance, pigment,
It may contain various optional components such as dyes.

Surfactants Bleaching compositions suitable for use in the woven or knitted bleaching method of the present invention are preferably:
It is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof. Here, the surfactant is present in a concentration of less than 5%, more preferably 0.1-4%, most preferably 1-3%.

Suitable anionic surfactants for use in the composition include water soluble salts or acids of formula ROSO ₃ M, where R is preferably a C ₁₀ -C ₂₄ hydrocarbon, preferably Is alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component,
More preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation, such as an alkali metal cation (eg sodium, potassium, lithium), or an ammonium or substituted ammonium (eg methyl-, dimethyl-, and trimethyl-ammonium). Cations, and quaternary ammonium cations such as tetramethylammonium, and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof). . Generally, C ₁₂ -C ₁₆ alkyl chains are preferred for low wash temperatures (eg, below about 50 ° C.) and C ₁₆ -C ₁₈ alkyl chains are preferred for high wash temperatures (eg, above about 50 ° C.).

[0037]   Other anionic surfactants suitable for use in the present invention include those of formula RO (A)_m
SO₃There is a water-soluble salt or acid of M, where R is C_Ten-C_{twenty four}Has an alkyl component
Non-substituted C_Ten-C_{twenty four}Alkyl or hydroxyalkyl, preferably C₁₂−
C₂₀Alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈Archi
Or hydroxyalkyl, A is an ethoxy or propoxy unit, m
Is greater than 0, usually between about 0.5 and about 6, and more preferably between about 0.5 and about 3.
In between, M is H or a cation, eg a metal cation (eg sodium, potassium
Aluminum, lithium, calcium, magnesium), ammonium or substituted ammonium
It is a nickel cation. Alkyl ethoxylated sulfates as well as alkyl propoxides
Xylated sulfate can also be used. Specific examples of substituted ammonium cations include
Cyl-, dimethyl-, and trimethyl-ammonium, and tetramethylammonium
Quaternary ammonium cations, such as, and dimethylpiperidinium, and
Alkanolamines such as ethylamine, diethylamine, triethylamine
There are such cations of origin, as well as mixtures of these. For example of surfactant
Is C₁₂-C₁₈Alkyl polyethoxylate (1.0) sulfate (C₁₂-C ₁₈ E (1.0) M), C₁₂-C₁₈Alkyl polyethoxylate (2.25) sulphate
Fate (C₁₂-C₁₈E (2.25) M), C₁₂-C₁₈Alkyl polyethoxy
(3.0) Sulfate (C₁₂-C₁₈E (3.0)) and C₁₂-C₁₈Al
Kill polyethoxylate (4.0) sulfate (C₁₂-C₁₈E (4.0) M)
In the formula, M is appropriately selected from sodium and potassium.

Other surfactants suitable for use in the present invention include alkyl sulfonates including water soluble salts or acids of formula RSO ₃ M, where R is a C ₆ -C ₂₂ straight chain or It is a branched or saturated alkyl group, preferably a C ₁₂ -C ₁₈ alkyl group, more preferably a C ₁₄ -C ₁₆ alkyl group, M is H or a cation, for example an alkali metal cation (eg sodium). , Potassium, lithium), or ammonium or substituted ammonium (eg, methyl-, dimethyl-, and trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium, and dimethylpiperidinium cations, and ethylamine, diethylamine, triethylamine. Quaternary ammonium derived from alkylamines such as Thione, and there are the mixtures thereof).

Alkylaryl sulfonates suitable for use in the present invention include those of the formula RSO ₃
There is a water-soluble salt or acid of M, wherein R is a C ₆ -C ₂₂ straight chain or branched saturated or unsaturated alkyl group, preferably a C ₁₂ -C ₁₈ alkyl group, more preferably Aryl substituted with a C ₁₄ -C ₁₆ alkyl group, preferably benzyl, M is H or a cation such as an alkali metal cation (eg sodium, potassium, lithium, calcium, magnesium etc.), or an ammonium or substituted ammonium (eg Methyl-, dimethyl-, and trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium, and dimethylpiperidinium cations, and ethylamine, diethylamine,
There are such quaternary ammonium cations derived from alkylamines such as triethylamine, as well as mixtures thereof).

The alkyl sulfonates and alkyl aryl sulfonates used in the present invention include primary and secondary alkyl sulfonates and primary and secondary alkyl aryl sulfonates. Here, “secondary C ₆ -C ₂₂ alkyl or C ₆ -C ₂₂ alkylaryl sulfonate” means that in the formula defined above, the SO ₃ M or aryl-SO ₃ M group is the other 2 of the alkyl chain. It is attached to the carbon atom (second carbon) of the alkyl chain between the carbons.

For example, a C ₁₄ -C ₁₆ alkyl sulfonate salt is commercially available from Hoechst under the trade name Hostapur (
(Registered trademark) SAS, C8-alkyl sulfonate sodium salt is Witco S
Commercially available from A to Witconate NAS 8®. An example of a commercially available alkylaryl sulfonate is lauryl aryl sulfonate from Su. Ma. Particularly preferred alkyl aryl sulfonates are from the Albright & Wilson trade name Nansa (
Alkyl benzene sulfonate available under the registered trademark).

Other anionic surfactants useful in cleaning applications can also be used. These can include salts (e.g., sodium, potassium, ammonium and mono-, - di - and substituted ammonium salts such as triethanolamine salt), C ₈ -C ₂₄ olefin sulfonates, for example, British Patent Specification 1, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of citric acid alkaline earth metal salts described in JP 082,179, C ₈ -C ₂₄ alkyl polyglycol ether sulfates (1
Containing up to 0 moles of ethylene oxide); alkyl ester sulfonates such as C ₁₄ -C ₁₆ methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulphates, alkylphenol ethylene oxide ether sulphates, paraffin sulphonates, alkyl phosphates,
Isethionates such as acyl isethionates, N-acyl taurates, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (
In particular saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters), sulfates of alkylpolysaccharides such as sulfates of alkylpolyglycosides ( The following nonionic non-sulfated compounds), branched chain primary alkyl sulphates, formula RO (CH ₂ C
_{H 2 O) K CH 2 COO} - M + alkyl polyethoxy carboxylates (wherein R C ₈ -C ₂₂ alkyl, such as, k is an integer of 0, M is soluble salt-forming cation) . Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, resin acids present in tall oil and derived from tall oil and hydrogenated resin acids are also suitable. Further examples are "Surfactants and Detergents" (Vol. I and II by Schwartz, Perry) (Volumes I and II, Schwartz, Perry and Birch).
and Berch)). Various such surfactants have also been described in US Pat.
, 929,678 (issued December 30, 1975, Lauglin et al., Col. 23, line 58 to col. 29, line 23) (cited and included herein).

Other anionic surfactants particularly suitable for use in the present invention have 4 to 24, preferably 8 to 18, more preferably 8 to 16 carbon atoms in the alkyl chain. There are alkylcarboxylates and alkylalkoxycarboxylates, where alkoxy is propoxy and / or ethoxy, preferably ethoxy with a degree of alkoxylation of 0.5 to 20, preferably 5 to 15. Preferred alkyl alkoxy carboxylates for use in the present invention, Kao Chemical Gbmh commercial laureth 11 carboxylate trade name Akyposoft (R) 100 nV from _{(i.e., RO (C 2 H 4 O} ) 10 -CH 2 COONa , R = C ₁₂ -C ₁₄ ).

Suitable amphoteric surfactants for use in the present invention are amine oxide surfactants having the formula R ₁ R ₂ R ₃ NO, where each R ₁ , R ₂ and R ₃ is Independently, 1-3
It is a saturated, substituted or unsubstituted, straight or branched chain hydrocarbon of 0 carbon atoms. Particularly preferred amine oxide surfactants for use in the present invention are amine oxide surfactants having the formula R ₁ R ₂ R ₃ NO, where R ₁ is from 1 to 30,
Preferably a hydrocarbon chain having 6 to 20, more preferably 8 to 16 and most preferably 8 to 12 carbon atoms, wherein R ₂ and R ₃ are independently 1 to 4,
It is preferably a substituted or unsubstituted, straight-chain or branched hydrocarbon chain having 1 to 3 carbon atoms, and even more preferably a methyl group. R ₁ is a saturated, substituted or unsubstituted, straight or branched chain hydrocarbon. Amine oxide surfactants suitable for use in the present invention is a commercially available natural blend C ₈ -C ₁₀ amine oxides as well as C ₁₂ -C ₁₆ amine oxides, for example, from Hoechst.

Suitable bipolar ionic betaine surfactants for use in the present invention have both cationic hydrophilic groups, ie, quaternary ammonium groups, and anionic hydrophilic groups, over a relatively wide range of pH. Contained in the same molecule. Typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups such as sulphates, phosphonates and the like can be used. The general formula for the zwitterionic betaine surfactants used in the present invention is:

[Chemical 6] Is.

Wherein R ₁ is a hydrophobic group; R ₂ is hydrogen, C ₁ -C ₆ alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ alkyl group; R ₃ is C ₁ -C ₆ alkyl group, hydroxy Alkyl or another substituted C ₁ -C ₆ alkyl group capable of binding to R ₂ to form a ring structure with N, or a C ₁ -C ₆ sulfonate group; R ₄ is a cationic nitrogen atom and hydrophilic The group connecting the groups is usually alkylene, hydroxyalkylene, or 1-10
Is a polyalkoxy group containing 4 carbon atoms; X is a hydrophilic group which is a carboxylate or sulfonate group.

[0047]   Preferred hydrophobic group R₁Must contain a linking group such as an amide group or an ester group.
Aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted carbon capable of
It is a hydrogenated chain. More preferably R₁Is 1 to 24, preferably 8 to 18
More preferably, it is an alkyl group containing 10 to 16 carbon atoms. These simple
Pure alkyl groups are preferred from a cost and stability standpoint. However, the hydrophobic group R ₁ Is also the formula R_a-C (O) -NH- (C (R_b)₂)_mMay be an amide group of
R in the formula_aIs an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted carbon
Hydrogen fluoride chain, from 8 to 20, preferably up to 18, more preferably up to 16
An alkyl group containing a carbon atom, R_bIs from a hydrogen atom and a hydroxy group
M is 1 to 4, preferably 2 to 3, more preferably 3 and
(R_b)₂) There is only one hydroxy group in the residue.

[0048]   Preferred R₂Is a hydrogen atom or C₁-C₃Alkyl, more preferably methyl
Is. Preferred R₃Is C₁-C_FourCarboxylic acid group or C₁-C_FourSulfonate group, or
Is C₁-C₃Alkyl and more preferably methyl. Preferred R_FourIs (CH₂) _n In the formula, n is an integer of 1 to 10, preferably 1 to 6, and more preferably 1 to 3.
.   Some common examples of common betaines / sulfobetaines are described in US Pat. No. 2,082,
275, 2,702,279, 2,255,082, and
Used in the present specification.

Examples of particularly suitable alkyl dimethyl betaines are coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-
There are N, N-dimethyl-ammonia) acetate, 2- (N-coco N, N-dimethyl-ammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine and stearyl dimethyl betaine. For example, coconut dimethyl betaine is commercially available from Seppic under the tradename Amonyl® 265. Lauryl betaine is trade name Empigen BB / L from Albright & Wilson
(Registered trademark).

Examples of amidobetaines are cocoamidoethylbetaine, cocoamidopropylbetaine or C ₁₀ -C ₁₄ fatty acylamido propylene (hydropropylene) sulfobetaine. For example C ₁₀ -C ₁₄ fatty acyl amides propylene (hydro propylene) sulfobetaine is commercially available under the trade name from Sherex Company "Varion CAS (R) sulfobetaine". A further example of betaine is lauryl-imino-dipropionate, which is commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®.

Cationic surfactants suitable for use in the present invention include quaternary ammonium,
Includes derivatives of phosphonium, imidazolium and sulfonium compounds. Cationic surfactants suitable for use in the present invention are quaternary ammonium compounds, wherein the one or two hydrocarbon groups attached to the nitrogen atom have from 6 to 30 carbon atoms, preferably 10 to Saturated straight or branched chain alkyl groups of 25 carbon atoms, more preferably 12 to 20 carbon atoms, with other hydrocarbon groups attached to the nitrogen atom (
That is, three when one hydrocarbon group is a long-chain hydrocarbon group as described above, or two when two hydrocarbon groups are long-chain hydrocarbon groups as described above), independently, 1-4
A substituted or unsubstituted, linear or branched alkyl chain of 1 carbon atom, preferably 1 to 3 carbon atoms, more preferably a methyl group. Suitable quaternary ammonium compounds for use in the present invention are non-chlorine / non-halogen quaternary ammonium compounds. The counterion used in the quaternary ammonium compound is compatible with any peracid and is selected from the group of methyl sulphate or methyl sulphonate.

Particularly suitable for use in the present invention are trimethyl quaternary ammonium compounds such as myristyl trimethyl sulphate, cetyl trimethyl sulphate and / or tallow trimethyl sulphate. Such trimethyl quaternary ammonium compounds are commercially available from Hoechst or from Albright & Wilson under the EMPIGEN CM®. Among them, nonionic surfactants, alkoxylated nonionic surfactants, and especially ethoxylated nonionic surfactants are suitable for use. Particularly preferred nonionic surfactants for use in the present invention are capped alkoxylated nonionic surfactants as they can also provide a foam control effect.

Suitable capped alkoxylated nonionic surfactants for use in the present invention have the formula:

[Chemical 7] It is represented by. In the formula, R ₁ is a C ₈ -C ₂₄ linear or branched alkyl or alkenyl group, an aryl group, an alkaryl group, preferably R ₁ is a C ₈ -C ₁₈ alkyl or alkenyl group, more preferably C _10-. A C ₁₅ alkyl or alkenyl group, even more preferably a C ₁₀ -C ₁₅ alkyl group; wherein R ₂ is a C ₁ -C ₁₀ straight or branched chain alkyl group, preferably C ₂ -C ₁₀
A linear or branched alkyl group; wherein R ₃ is a C ₁ -C ₁₀ alkyl or alkenyl group, preferably a C ₁ -C ₅ alkyl group, more preferably methyl; wherein n and m are , Independently, 1-20, preferably 1-10, more preferably 1
An integer in the range of 5; or a mixture thereof.

These surfactants are commercially available from BASF under the trade name Plurafac®, from HOECHST under the trade name Genapol®, and from ICI under the trade name Symperonic®. The preferred capped non-ionic alkoxylated surfactants described above are from Hoechst under the tradename Genapol® L 2.5NR and from BASF under the tradename Plurafac.
(Registered trademark).

Chelating Agents Compositions suitable for use in the woven and knit bleaching process of the present invention may contain a chelating agent as a preferred optional ingredient. Suitable chelating agents are selected from the group consisting of phosphonate chelating agents, aminocarboxylate chelating agents, other carboxylate chelating agents, polyfunctional substituted aromatic chelating agents, ethylenediamine N, N'-disuccinic acid, or mixtures thereof. Any of those known to those of skill in the art.

The presence of chelating agents contributes to further promoting the chemical stability of the composition. Chelating agents are desirable in the composition because they increase the ionic strength of the composition and increase stain removal and bleaching performance on various surfaces.

Suitable phosphonate chelating agents for use in the present invention include ethane-1-hydroxy-diphosphonic acid alkali metal salts (HEDP), alkylene poly (alkylenephosphonates) and aminoaminotri (methylenephosphonic acid) (ATMP). )
Aminophosphonate compounds containing Nitrilotrimethylenephosphonate (NTP
), Ethylenediaminetetramethylenephosphonate, and diethylenetriaminepentamethylenephosphonate (DTPMP). The phosphonate compounds may either be in their acid form or salts of cations that differ in some or all of their acid functional groups. Preferred phosphonate chelating agents for use in the present invention are
Diethylenetriamine pentamethylene phosphonate (DTPMP) and ethane-
1-hydroxy-diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.

Multifunctional substituted-aromatic chelating agents are also useful in the present compositions. See U.S. Pat. No. 3,812,044 (Connor et al., Issued May 21, 1974). Preferred compounds of this type in the acid form are 1,2-dihydroxy-3,5-
Dihydroxydisulfobenzene, such as disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine N,
N'-disuccinic acid or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts or mixtures thereof. Ethylenediamine N, N'-
Disuccinic acid, especially the (S, S) isomer, is described in US Pat. No. 4,704,233 (198).
November 3, 1995, Hartman and Perkins). Ethylenediamine N, N'-disuccinic acid has, for example, the trade name ssEDDS®, available from Palmer Research Laboratories.

Aminocarboxylates suitable for use in the present invention include both acid or alkali metal, ammonium, substituted ammonium salt forms, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-hydroxyethyl ethylenediamine triacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylene tetraamine hexa-acetate, ethanol diglycine, propylene diamine tetraacetic acid (PDTA), and methylglycine di-acetic acid (MG
DA) Particularly suitable aminocarboxylates for use in the present invention are, for example, diethylenetriaminepentaacetic acid, trade name Trilon FS® from BASF.
And commercially available propylenediaminetetraacetic acid (PDTA) and methylglycine di-acetic acid (MGDA). Further, the carboxylate chelating agents used in the present invention include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.

[0061]   Other chelating agents used in the present invention have the formula:

[Chemical 8] belongs to.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ independently represent —H, alkyl, alkoxy, aryl, aryloxy, —Cl, —Br, —NO ₂ , —C (O) R. 'And -S
O ₂ R ″ is selected from the group consisting of; R ′ is selected from the group consisting of —H, —OH, alkyl, alkoxy, aryl and aryloxy; R ″ is alkyl, alkoxy, aryl and aryloxy. Selected from the group consisting of; R ₅ , R ₆ ,
R ₇ and R ₈ are independently selected from the group consisting of —H and alkyl.

Particularly preferred chelating agents for use in the present invention are aminoaminotri (methylenephosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamine-N, N-disuccinic acid, and mixtures thereof. Generally, compositions suitable for use in the woven or knitted bleaching method of the present invention are up to 5% by weight of the total composition, preferably 0.01 to 1.5% by weight, more preferably 0.01 to 1.5% by weight.
It contains 0.5% by weight of chelating agents or mixtures thereof.

Radical Scavengers: Bleaching compositions suitable for use in the woven and knit bleaching methods of the present invention may contain radical scavengers or mixtures thereof. Radical scavengers suitable for use in the present invention include the well-known substituted mono- and di-hydroxybenzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof. Preferred such radical scavengers for use in the present invention include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-ter.
t-butylhydroquinone, tert-butyl-hydroxyanisole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine, 1,1,
3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
There are n-propyl gallic acid and mixtures thereof, highly preferred is di-t
ert-butylhydroxytoluene. Radical scavengers such as N-propyl gallic acid are commercially available from Nipa Laboratories under the tradename Nipanox S1®.
It is commercially available at. When using radical scavengers in the present invention,
Included up to 10% by weight of the total composition, preferably 0.001-0.5% by weight. The presence of radical scavengers contributes to the chemical stability as well as the safety profile of the bleach composition used in the present invention.

Test Method: For various types of bleachable stain stains, the bleaching performance may be evaluated by the following method. A suitable test method for bleaching performance on soiled woven and knitted fabrics is as follows: First, the typical step (b) is applied to a washing machine (eg 225 g of conventional detergent such as Arie).
l Future® is introduced into the detergent dispenser of a conventional washing machine such as the Sangiorgio Exacta 352ZX® to perform a wash cycle with the soiled woven or knitted fabric or a hand soaking operation (eg Usually done by contacting a conventional detergent, for example Ariel a mano®, with a soaking solution obtained by diluting with a dilute concentration of 140 ml / 10 liter of water-normal soaking times are from 1 minute to several hours. ). The bleaching composition described herein is then typically diluted to a dilution concentration of 1 to 100 ml / L, preferably 20 ml / L (
(Composition: water), then soak the woven or knitted fabric already subjected to step (b) above in the bleach composition for 20 minutes to 6 hours (ie step (a)), then rinse ( Step (c)). Alternatively, the bleach composition can be machine washed, usually 1 to 100 ml.
It can be used at a diluted concentration of / L (composition: water). 30 or more for woven and knitted fabrics that are soiled in the washing machine
It is bleached for 10 to 100 minutes at a temperature of 90 ° C. and then rinsed. For example, woven / knitted fabric / swatches soiled with tea, coffee, etc. are commercially available from EMC Co. Inc.

The bleaching performance is evaluated by side-by-side comparison with the soiled woven or knitted fabric, which was only cleaned with the detergent composition in step (b) and which did not use step (a).
A visual rating is used, with panel unit (psu) differences ranging from 0-4. The same test method can be used to evaluate the stain removal performance, except that the woven or knitted fabric is soiled with different types of stains such as enzymes and / or oils.

[0067]

【Example】

The following compositions were prepared by mixing the listed ingredients in the listed proportions (wt% unless otherwise specified). These compositions are suitable for use in the "bleaching stage" of the bleaching process of the present invention.

[0068]

[Table 1]

Akyposoft 100 NV® is a C ₁₂ -C ₁₄ alkylethoxy 10 carboxylate commercially available from Kao Chemicala Gmbh. Witkonate NAS 8® is an alkyl sulfonate commercially available from Witco AS. HEDP is an ethane-1-hydroxy-diphosphonate commercially available from Monsanto in the Dequest® series. PAP is a phthalimidoperoxyhexanoic acid commercially available from Ausimont under the tradename Euroco®. Cabopol® ETD 2623 and 2991 are polymers available from BF Goodrich. The following composition is representative of a granular detergent composition suitable for dilution with water to provide an alkaline solution suitable for use in the first step (alkali step) of the process of the invention.

[0070]

[Table 2]

[0071]

[Table 3]

The following compositions are representative of liquid detergent compositions suitable for dilution with water to provide a suitable alkaline solution for use in the first step of the woven and knit bleaching process of the present invention. .

[0073]

[Table 4]

[0074] LAS: Straight chain C₁₂Sodium alkylbenzene sulfonate TAS: Tallow Sodium Alkyl Sulfate QAS: R₂． N⁺(CH₃)₂(C₂H_FourOH) R₂= C₁₂~ C₁₄ TFAA: C₆~ C₁₈Alkyl N-methyl glucamide TPKFA: C₁₂~ C₁₄Topped whole cut fatty acid NaSKS-6: Formula δ-Na₂Si₂O_FiveCrystalline layered silicate Carbonate: Anhydrous sodium carbonate with a particle size of 200 to 900 μm Bicarbonate: anhydrous sodium bicarbonate with a particle size of 400-1200 μm STPP: anhydrous sodium tripolysulfate MA / AA: 1: 4 maleic acid / acrylic acid copolymer having an average molecular weight of about 80,000
Zeolite A: Formula Na with primary particle size ranging from 0.1 to 10 micrometers ₁₂ (AlO₂SiO₂)₁₂． 27H₂Hydrated aluminosilicate sodium represented by O
Mu

Citrate: Trisodium citrate dihydrate with a particle size distribution of 425-850 μm and an activity of 86.4% PB1: Empirical formula NaBo2. H2O2 anhydrous sodium perborate monohydrate bleach PB4: anhydrous sodium perborate tetrahydrate TAED: tetraacetylethylenediamine photoactive bleach: zinc sulphonated phthalocyanine CMC encapsulated in dextrin soluble polymer CMC: Sodium carboxymethyl cellulose HEDP: 1,1-hydroxyethanediphosphonic acid DETPMP: Diethylenetriamine penta (methylenephosphonic acid), commercially available from Monsanto under the trade name Dequest 2060. PVNO: Poly (4-vinylpyridine) -N-oxide PVPVI: Poly (4-vinylpyridine) -N-oxide / copolymer of vinylimidazole and vinylpyrrolidone Silicone antifoam agent: Polydimethylsiloxane foam control agent and dispersant Siloxane-oxyalkylene copolymer, as a foam control agent to dispersant ratio of 10: 1 to 100
: 1 SRP 2: diethoxylated poly (1,2-propylene terephthalate) short block polymer PPT: 10-phenothiazine propionate BUS: butyl syringate sulfate: anhydrous sodium sulfate

Example of Woven / Knit Bleaching Method of the Present Invention The present invention is explained by the following woven / knit bleaching method. Any of the following "alkaline stage" / "bleaching stage" combinations are suitable, provided that the "alkaline stage" precedes the "bleaching stage".

[0077]

[Table 5]

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Table 8]

“During the main wash ^* ” of the bleaching stage means that the bleaching composition is introduced directly into the detergent dispenser in the absence of detergent, or into the bleach dispenser if the machine is of such construction, and the wash cycle is It should be understood that it is done with the bleach composition without the composition. The alkaline detergent used in the woven and knit bleaching method exemplified above is any conventional detergent composition available on the market, for example Ariel future, Dash when used in a washing machine.
future (registered trademark), when used for hand washing, there is Ariel a Mano (registered trademark). The peracid-containing compositions used in these methods are the compositions I-V exemplified above.
Is any of. Any washing machine including US type or Japanese type as well as European type may be used. An example is San Giorgio Exacta 252 ZX. All of the above methods provide woven and knit fabric and color safe, excellent bleaching performance and efficient stain removal performance when bleaching the woven and knit fabric as indicated above.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06L 3/16 D06L 3/16 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU) , TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, D. , EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR , TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Di Capua, Gloria Italy, 00004 Ardea, Via, Corone, Boreale 131 (72) Inventor Dresco, Pierre Antoine Italy , 00165 Rome, Via, San, Silverio 23 (72) Inventor Schalla, Stefano Italy, 00128 Rome, Via, Effe, Bi, Rastrelli 81 F-term (reference) 4H003 AB05 AB19 AC08 DA01 EB10 EB24 EB30 EB42 EB46 FA08 FA15 FA28 FA42

Claims (15)

[Claims] 1. A method of cleaning a woven or knitted fabric with a bleaching composition and a detergent composition, comprising the following individual steps: (a) a bleaching composition containing a preformed peroxycarboxylic acid. Contacting, (b) contacting the woven or knitted fabric with a detergent composition, and (c) rinsing the woven or knitted fabric with water. 2. The method of claim 1, wherein step (a) is performed prior to step (b). 3. The method of claim 1, wherein step (b) is performed prior to step (a). 4. The preformed peroxycarboxylic acid has the general formula: (Wherein R is a C _1-20 alkyl group, and A, B, C and D are independently alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxyl, sulfate, sulfonate, aldehyde or their Which is a substituent or a hydrogen atom individually selected from the group consisting of the mixture of 5. The preformed peroxycarboxylic acid has the general formula: (Wherein R is a C _1-4 alkyl group and n is an integer of 1 to 5). 6. The method according to claim 5, wherein the preformed peroxycarboxylic acid is represented by the general formula where R is CH ₂ and n is 5. 7. The bleach composition has a pH value of 1 to 6.5.
The method described in any one of. 8. The method according to claim 1, wherein the bleaching composition contains a surfactant in a concentration of less than 5% by weight of the composition. 9. The method according to claim 1, wherein the preformed peroxycarboxylic acid is solid and substantially water-insoluble. 10. The process according to claim 1, wherein the bleaching composition additionally contains a suspending agent which consists of at least one, preferably at least one polymer. 11. The method according to claim 1, wherein the detergent composition has an alkaline pH of greater than 7. 12. The method according to claim 1, wherein the detergent composition contains more than 5% of a surfactant. 13. The method according to claim 1, which is carried out in a washing machine having at least one rinse cycle and a washing cycle. 14. The step (a) during at least one rinse cycle of the washer.
The method according to claim 13, wherein 15. The method according to claim 13 or 14, wherein step (b) is carried out during the washing cycle of the washing machine.