JP2002535446A - Method of treating fabric with laundry detergent additives - Google Patents

Abstract

  (57) [Summary] Creating an aqueous bath containing a liquid composition containing a peroxygen bleach, a builder, and a modified polycarboxylate co-builder, water, and a conventional laundry detergent dissolved or dispersed in water; A method for treating fabric, comprising the step of contacting with an aqueous bath. Further, a peroxy bleach-containing agent, wherein the fabric is treated using a builder and a modified polycarboxylate co-builder in a peroxygen bleach-containing laundry detergent additive, thereby achieving a soil removal and / or bleaching effect. Use of builders and modified polycarboxylate co-builders in laundry detergent additives.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

TECHNICAL FIELD The present invention relates to a method of treating a fabric with a composition containing a liquid peroxygen bleach. The composition is suitable for use as a laundry detergent additive in addition to conventional laundry detergents. More specifically, the compositions of the present invention are suitable for use on a variety of fabrics to achieve soil removal and / or bleaching performance.

[0002]

[Prior art]

Background Bleach-containing compositions for fabric bleaching are well known in the art. Liquid peroxygen bleach-containing compositions have been extensively described in the art, particularly as laundry detergents, laundry detergent additives or laundry pre-treatment agents for laundry applications.

In fact, such liquid peroxygen bleach-containing compositions are particularly difficult to remove with conventional machine washing, such as oil, coffee, tea, grass juice, mud / clay containing soils, “
It is known to be used as a laundry detergent additive to facilitate the removal of problematic "soils" and stains / stains / soils covered with hard skin.

However, there are some restrictions on the convenience of using this peroxygen bleach-containing composition as a laundry detergent additive. It is well known from consumer surveys that the color, stain and stain removal performance of the composition should be further improved.

[0005]

[Problems to be solved by the invention]

Thus, it is an object of the present invention to provide a method of treating fabric using a laundry detergent additive that provides a wide range of coloring and stains, improved coloring and stains in general, stain removal performance, and at the same time provides excellent bleaching performance. To offer.

[0006]

[Means for Solving the Problems]

It has now been found that this object can be achieved by a method of treating fabric with a laundry detergent additive, which is a liquid composition containing a peroxygen bleach, a builder and a co-builder as described herein. .

[0007] In fact, such compositions, when used as laundry detergent additives, are more oily and / or enzymatically soiled than the same composition with different builder systems or the same composition without builder systems. And the ability to remove various types of coloring, stains, and stains.

[0008] The compositions described herein are also advantageous in providing excellent bleaching performance.

A further advantage of the compositions according to the invention is that the compositions according to the invention exhibit their performance under various conditions, ie in hard or soft water, as well as undiluted or diluted. What you can do.

[0010] Yet another advantage of the compositions of the present invention is that the compositions of the present invention can be used in natural fabrics (eg, cotton, viscose, linen, silk, and wool), synthetic fabrics (eg, fabrics made of synthetically derived polymer fibers), and It is suitable for bleaching any type of fabric, including fabrics made of both natural and synthetic fibers.

[0011] BACKGROUND EP-A-0 686 691 and No. EP-A-0 844 302 items, peroxygen bleaches and citrate or citric suitable for use as a laundry detergent additive or fabric pretreatment agent Disclosed are compositions containing an acid. None of the above references disclose a method for fabric bleaching using a composition containing a peroxygen bleach, a builder and a modified polycarboxylate co-builder.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a process for making an aqueous bath containing a liquid composition containing a peroxygen bleach, a builder and a modified polycarboxylate co-builder, and water, a conventional laundry detergent dissolved or dispersed in water. And then contacting the fabric with the aqueous bath.

The present invention further provides for the treatment of fabrics using builders and modified polycarboxylate co-builders in laundry detergent additives containing peroxygen bleaches, thereby removing color and stains, removing stains and Also included are methods of using builders and modified polycarboxylate co-builders in peroxygen bleach-containing laundry detergent additives to achieve a bleaching effect.

[0014] The fabric processing method according to a detailed description fabric treatment The present invention relates to a peroxygen bleach, a builder and modified polycarboxylate co - a liquid composition containing a builder, water and dissolved or dispersed in water conventional Making an aqueous bath containing the laundry detergent, and then contacting the fabric with the aqueous bath.

[0015] In this method, the treated fabric is contacted with a liquid composition as defined herein. This treatment is performed by adding a liquid composition as defined herein to a washing liquid produced by dissolving or dispersing a conventional laundry detergent in water, that is, using the liquid composition according to the present invention in a so-called "laundry detergent". It is carried out according to a “complete (from the beginning to the end) washing mode” used as an “additive”. The dilution ratio of the liquid composition in the aqueous bath is usually up to 1:85 (composition: water), preferably up to 1:50, more preferably 1: 1.
: Up to 25. The fabric is then contacted with an aqueous bath containing the liquid composition and a conventional laundry detergent. Preferably, the fabric is finally rinsed.

In a preferred embodiment, the liquid composition is added undiluted to the aqueous bath.

“Conventional laundry detergent” means herein laundry detergent compositions currently available on the market. The laundry detergent composition may be formulated as a powder or a liquid. Suitable laundry detergent compositions are, for example, dash futur (
DASH futur) (registered trademark), DASH liquid (registered trademark)
And products sold under the trade name ARIEL® or TIDE®.

In a preferred embodiment, the conventional laundry detergent described herein comprises at least one surfactant.

The contact between the aqueous bath described herein and the fabric can be effected by a washing machine or simply by hand washing.

Here, “processing” means to clean (clean). This is because the composition according to the invention achieves excellent removal performance against a wide range of stains and stains on various surfaces, mainly due to the presence of the builder and the co-builder as defined by the invention, as well as of the invention. This is because the composition achieves excellent bleaching performance mainly due to the presence of the peroxygen bleach.

“Undiluted” means that the liquid composition is added to the aqueous bath without any dilution, ie, the liquid composition is added to the aqueous bath as described herein. I want to be understood.

Liquid Composition The composition according to the invention is a liquid composition, not a solid composition or a gas composition. "Liquid" as used herein also includes compositions in gel or paste form.

Thus, a preferred composition of the present invention comprises a 4 cm spindle (10-100
Viscosities of 1 centipoise (cps) or more at 20 ° C. as measured using a CSL ² 100® rheometer at 20 ° C. with a linear increment of dyne / cm ² ), more preferably It has a viscosity of 10 to 5000 cps, more preferably 10 to 2500 cps.

The liquid composition according to the invention preferably has a pH of up to 9, more preferably 2 to 7
PH, most preferably a pH of 2-6. In a preferred embodiment, the liquid compositions of the present invention are formulated in a neutral to acidic pH range, which contributes to the chemical stability of the composition and the soil removal performance of the composition. The pH of the composition can be adjusted with acidifying agents or mixtures thereof known to those skilled in the art. Examples of acidifying agents include inorganic acids,
For example, sulfuric acid.

Peroxygen bleach The composition of the present invention comprises a peroxygen bleach or a mixture thereof as a first essential component. In fact, the presence of a peroxygen bleach contributes to the excellent bleaching effect of the composition.

Suitable peroxygen bleaches for use in the compositions of the present invention include hydrogen peroxide; water-soluble hydrogen peroxide source materials; organic or inorganic peracids; hydroperoxides; diacyl peroxides; Selected from the group consisting of mixtures.

[0027] Hydrogen peroxide source material for use in the composition of the present invention refers to any compound that produces perhydroxyl ions on contact with water. Suitable water-soluble hydrogen peroxide source materials for use in the present invention include percarbonates, perborates, persilicates and mixtures thereof.

Suitable diacyl peroxides for use in the compositions of the present invention include aliphatic diacyl peroxides, aromatic diacyl peroxides and aliphatic-aromatic diacyl peroxides and mixtures thereof.

[0029] Suitable aliphatic diacyl peroxides for use in the compositions of the present invention include dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, or mixtures thereof. Aromatic diacyl peroxides suitable for use in the present invention include, for example, benzoyl peroxide. Suitable aliphatic-aromatic diacyl peroxides for use in the present invention include, for example, lauroylbenzoyl peroxide. Such diacyl peroxides have the advantage of being particularly safe for fabrics and colors and of providing excellent bleaching performance when used in any laundry application.

[0030] Organic or inorganic peracids suitable for use in the compositions of the present invention include persulfates such as monopersulfate (peroxomonosulfate); peroxyacids such as diperoxydidodecanoic acid (DPDA). Magnesium perphthalate; perlauric acid; phthaloylamide peroxycaproic acid (PAP); perbenzoic acid and alkyl perbenzoic acid; and mixtures thereof.

Hydroperoxides suitable for use in the compositions of the present invention include t-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-
2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, t-amyl hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide and mixtures thereof. Such hydroperoxides have the advantage of being particularly safe for textiles and colors and of providing excellent bleaching performance when used in any laundry application.

[0032] Suitable peroxygen bleaches for use in the compositions of the present invention include hydrogen peroxide; water-soluble hydrogen peroxide source materials; organic or inorganic peracids; hydroperoxides; and diacyl peroxides; Is selected from the group consisting of: More suitable peroxygen bleaches for use herein are selected from the group consisting of hydrogen peroxide and diacyl peroxide and mixtures thereof. Further suitable peroxygen bleaches are selected from the group consisting of hydrogen peroxide, aliphatic diacyl peroxides, aromatic diacyl peroxides, and aliphatic-aromatic diacyl peroxides and mixtures thereof.

Usually, the composition of the present invention comprises from 0.01 to 20% by weight of the total composition, preferably from 0.3 to 20%.
It may contain up to 15% by weight, more preferably 0.5 to 10% by weight, of a peroxygen bleach or a mixture thereof.

Builders The composition of the present invention contains one or more builders as a second essential component. Suitable builders are selected from the group consisting of organic acids and salts thereof; polycarboxylates; and mixtures thereof. Typically, builders have a calcium chelating constant (pKCa) of at least 3. The pKCa value of the builder or a mixture thereof is determined using a 0.1 molar NH ₄ Cl—NH ₄ OH buffer (pK measured at 25 ° C.).
H is a value measured with a standard calcium ion electrode using 10) and a 0.1% solution of the builder or a builder thereof.

Examples of builders include organic acids such as citric acid, lactic acid, tartaric acid, oxalic acid,
Malic acid, monosuccinic acid, disuccinic acid
), Oxydisuccinic acid, carboxymethyloxysuccinic acid, diglycolic acid, carboxymethyltartronate, ditaltronate, and other organic acids and mixtures thereof.

[0036] Suitable salts of organic acids include alkaline salts, preferably sodium or potassium salts, alkaline earth metal salts, ammonium salts or alkanolamine salts.

The organic acids and salts thereof as described above are used in Jungbunzlaur
), Commercially available from Haarman & Reimen, Sigma-Aldrich or Fluka.

[0038] Other suitable builders include various polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound containing multiple carboxylate groups, preferably at least three carboxylate groups. The polycarboxylate builder can usually be added to the composition in its acid form, but can also be added in neutralized salt form or "overbased". When used in salt form, alkali metal salts, such as sodium, potassium and lithium salts, or alkanolammonium salts are preferred.

Useful polycarboxylates include homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid.

Other useful polycarboxylate builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-tri Sulfonic and carboxymethyloxysuccinic acids, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as nitrilotriacetic acid, and polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1 , 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and their water-soluble salts.

Suitable polycarboxylates are available from Rohm & Haas as Norasol® or Acusol®
It is commercially available under the trade name.

Suitable builders in the present invention are citric acid; tartaric acid; tartrate monosuccinate; tartrate disuccinat
e); lactic acid; oxalic acid; and malic acid; and mixtures thereof. Further preferred builders in the present invention are selected from the group consisting of citric acid; tartaric acid; tartaric acid monosuccinate; tartaric acid disuccinate; and malic acid; and mixtures thereof. The most preferred builders are selected from the group consisting of citric acid, tartaric acid, tartaric acid monosuccinate, tartaric acid disuccinate and mixtures thereof.

The compositions according to the invention usually comprise up to 40% by weight of the total composition, preferably from 0.01 to 2%.
5% by weight, more preferably 0.1-15% by weight, most preferably 0.5-10% by weight
May be contained.

Modified polycarboxylate co-builder The composition of the present invention contains a modified polycarboxylate co-builder as a third essential ingredient. The term "polycarboxylate" refers to a compound having multiple carboxylate groups, preferably at least three.

“Modified polycarboxylate” means a polycarboxylate compound, that is, the compound is modified with a functional group, such as a phosphono group, at at least one end of the polycarboxy chain. Suitable modified polycarboxylate co-builders are polycarboxylates with phosphono end groups.

“Phosono end group” means a phosphono functional group represented by the formula:

[0047]

Embedded image

Wherein each M is independently H or a cation, and preferably both M are both H.

Examples of suitable modified polycarboxylates having phosphono end groups are copolymers of acrylic acid with maleic acid having phosphono end groups and homopolymers of acrylic acid having phosphono end groups.

Suitable modified polycarboxylates are phosphonic / phosphono-terminated copolymers of acrylic acid and maleic acid represented by the general formula:

[0051]

Embedded image

(The above general formula is an average molecular weight of 1,000 to 100,000, preferably 1.0
It has an average molecular weight of 00 to 20,000, more preferably an average molecular weight of 1,000 to 10,000, most preferably an average molecular weight of 1,500 to 5,000, and n in the above general formula is 10 mol. % To 90 mol%, preferably 80 mol%, and m is 10 mol% to 90 mol%, preferably 20 mol%.

Accordingly, an example of a suitable modified polycarboxylate is represented by the following formula, wherein n is 80 mol%, m is 20 mol%, and the average molecular weight is 2,000 acrylic acid and maleic acid (80 / 20) is a copolymer having phosphon / phosphono end groups with:

[0054]

Embedded image

Such modified polycarboxylates are commercially available from Rohm and Haas under the trade name Acusol 425®, Acusol 420® or Acusol 470® Available at

Usually, the compositions according to the invention comprise up to 40% by weight of the total composition, preferably from 0.01 to 2%.
It may contain 5%, more preferably 0.1 to 15%, most preferably 0.5 to 5% by weight of modified polycarboxylate co-builder.

When used as a laundry detergent additive, significant synergy between the builder and the modified polycarboxylate co-builder in peroxygen bleach-containing compositions was observed. This synergy results in improved soil removal for a variety of soils, from particulate soils to non-particle soils, and from hydrophobic soils to hydrophilic soils, both on hydrophilic and hydrophobic fabrics. Performance is obtained.

The present invention relates to the use of compositions containing the peroxygen bleaches, builders and co-builders described herein as oil stains (eg, lipstick, olive oil, mayonnaise, vegetable oils, etc.) when used as laundry detergent additives. It is based on the finding that it shows excellent soil removal performance against various types of soil including sebum, make-up and enzymatic soil. This soil removal performance is improved compared to the soil removal performance provided by using a similar composition without the builder system or a similar composition containing a different builder system as a laundry detergent additive. .

In addition, the compositions described herein also exhibit excellent bleaching performance due to the presence of the peroxygen bleach.

The stain removal performance can be evaluated for various types of stains by the following test methods. A suitable test method for evaluating the soil removal performance of soiled fabrics under laundry conditions is as follows: A conventional laundry detergent [DASH FUTUL (DASH) without diluting the peroxygen bleach-containing composition according to the invention. futur) ® or Dash Liquid (DA)
SH liquid) @] into a standard washing machine. Soiled fabrics (eg, fabrics stained with greasy or enzymatic stains) are treated in the washing machine by standard operation of the washing machine. After treatment, the fabric is similarly soiled with a peroxygen bleach-containing composition containing no builder system or a peroxygen bleach-containing composition containing a builder system different from the builder system described herein, as described above. And compare it to the one processed.

A visual rating ranging from 0 to 4 is used to determine the psu of each individual test judge individual. The bleaching performance can be evaluated in the same manner as the evaluation for the soil removal performance only when the stains on the used fabric are bleachable stains such as coffee and tea.

Optional Ingredients The composition according to the present invention may further comprise various other optional ingredients, such as chelating agents, surfactants, stabilizers, bleach activators, soil sedimentation inhibitors, polyamine polymers for soil sedimentation prevention, polymer soil release. Agents, foam reducing systems, radical scavengers, catalysts, dye transfer agents, brighteners (whitening agents), fragrances, hydrotropes (hydrotropes), solvents, pigments, dyes, and the like.

Surfactants The compositions of the present invention may further comprise surfactants, including nonionic, zwitterionic, anionic, cationic and / or amphoteric surfactants or surfactants thereof. May be contained.

In a preferred embodiment of the present invention, the composition of the present invention contains a nonionic surfactant or a zwitterionic betaine surfactant or a mixed surfactant thereof.

[0065] In another preferred embodiment of the present invention, the composition of the present invention contains a sulfonated anionic surfactant. More preferably, the composition of the present invention contains a second surfactant selected from the group consisting of a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant and a mixed surfactant thereof.

The composition of the present invention is generally used in an amount of 0.01 to 30% by weight of the total composition, preferably 0.1 to 30% by weight.
Surfactants can be contained at ２５25% by weight, more preferably 0.5-20% by weight.

Examples of suitable nonionic surfactants include alkoxylated nonionic surfactants.
I can do it. Suitable alkoxylated nonionic surfactants include those of the formula RO-
(C_TwoH_FourO)_nAn ethoxylated nonionic surfactant represented by H (where R is C₆-C _{twenty two} Alkyl chain, or C₆-C₂₈In the alkylbenzene chain, n is 0 to 20, preferably
Is 1 to 15, more preferably 2 to 15, and most preferably 2 to 12. Book
A preferred R chain for use in the invention is C₈-C_{twenty two}Is an alkyl chain. Specified here
Instead of ethoxylated nonionic surfactant, propoxylated nonionic surfactant
And ethoxylated / propoxylated nonionic surfactants or together
Can be used.

Suitable ethoxylated nonionic surfactants are represented by the formula above and less than 16,
Preferably an ethoxylated nonionic surfactant having an HLB (hydrophilic / lipophilic ratio) of less than 15, more preferably less than 14. These ethoxylated nonionic surfactants were found to exhibit good oil stain removal properties.

Accordingly, suitable ethoxylated nonionic surfactants for use in the present invention are
Dobanol® 91-2.5 (HLB = 8.1; R is C₉Al
Kill chain and C₁₁A mixed chain with an alkyl chain, n is 2.5) or lutesol (Lute
nsol) (R) TO3 (HLB = 8; R is C₁₃Alkyl chain, n is 3), and
Is Lutensol® AO3 (HLB = 8; R is C₁₃Archi
Le chain and C_FifteenMixed chain with alkyl chain, n is 3), or Tergitol
(Registered trademark) 25L3 (HLB = 7.7; R is C₁₂~ C_FifteenRange of alkyl chain length,
n is 3), or Dobanol (registered trademark) 23-3 (HLB = 8.1)
R is C₁₂Alkyl chain and C₁₃A mixed chain with an alkyl chain, n is 3), or
(Dobanol) 23-2 (HLB = 6.2; R is C₁₂Alkyl chain and C ₁₃ A mixed chain with an alkyl chain, n is 2) or Dobanol (registered trademark)
45-7 (HLB = 11.6; R is C₁₄Alkyl chain and C_FifteenMixed chain with alkyl chain
, N is 7), or Dobanol® 23-6.5 (HLB =
11.9; R is C₁₂Alkyl chain and C₁₃A mixed chain with an alkyl chain, n is 6.5),
Or Dobanol (registered trademark) 25-7 (HLB = 12; R is C₁₂Al
Kill chain and C_FifteenA mixed chain with an alkyl chain, n is 7) or Dobanol (
Registered trademark) 91-5 (HLB = 11.6; R is C₉Alkyl chain and C₁₁Alkyl chain
And n is 5), or Dobanol® 91-6 (H
LB = 12.5; R is C₉Alkyl chain and C₁₁A mixed chain with an alkyl chain, n is 6),
Or Dobanol® 91-8 (HLB = 13.7; R is C ₉ Alkyl chain and C₁₁A mixed chain with an alkyl chain, n is 8) or dobanol (Doban
ol) (registered trademark) 91-10 (HLB = 14.2; R is C₉~ C₁₁Mixing of alkyl chains
Conjugated chains, n is 10) or Dobanol® 91-12 (HL
B = 14.5; R is C₉~ C₁₁A mixed chain of alkyl chains, n is 12) or
Is a mixture of

[0070] Dobanol® 91-2.5 or Lutensol
nsol) (registered trademark) TO3, or Lutensol (registered trademark) AO
3, or Tergitol® 25L3, or Dobanol® 23-3, or Dobanol® 2
3-2, or Dobanol (R) 45-7, or Dobanol (R) 91-8, or Dobanol (R) 9
1-10 or Dobanol® 91-12 or mixtures thereof are suitable for use in the present invention.

[0071] These Dobanol® surfactants are available from SHELL
) Is available commercially. These Lutensol® surfactants are commercially available from BASF, and Tergitol® surfactants are commercially available from UNION CARBIDE. A suitable chemical method for preparing the alkoxylated nonionic surfactant for use in the present invention comprises condensing the corresponding alcohol with the desired proportion of alkylene oxide. Such methods are well known to those skilled in the art and are widely described in the art literature.

The composition of the present invention desirably comprises one of these ethoxylated nonionic surfactants or a mixture of ethoxylated nonionic surfactants with different HLB (hydrophilic-lipophilic ratio). In a preferred embodiment, the composition of the present invention is an ethoxylated nonionic surfactant represented by the above formula and having an HLB of up to 10, preferably less than 10, more preferably less than 9, ie, So-called hydrophobic ethoxylated nonionic surfactants) and represented by the above formula and greater than 10 and up to 16,
It preferably contains an ethoxylated nonionic surfactant having an HLB of 11 to 14 (ie, a so-called hydrophilic ethoxylated nonionic surfactant). In fact, in this preferred embodiment, the compositions of the present invention usually comprise from 0.01 to 15% by weight of the total composition.
Preferably 0.5 to 10% by weight of said hydrophobic ethoxylated nonionic surfactant and 0.01 to 15% by weight, preferably 0.5 to 10% by weight of said hydrophilic ethoxylated nonionic surfactant It contains. Mixtures of ethoxylated nonionic surfactants with such different HLBs are desirable because they allow optimal oil stain cleaning and removal performance for a wide range of oil stains with various hydrophobic / hydrophilic properties.

Other nonionic surfactants suitable for use in the present invention include polyhydroxyfatty acid amide surfactants represented by the following general formula or mixed nonionic surfactants thereof:

[0074]

Embedded image R ² —C (O) —N (R ¹ ) —Z

[0075] (wherein, R ¹ is H or C ₁ -C ₄ alkyl group, C ₁ -C ₄ hydrocarbon radical, 2-hydroxyethyl group, 2-hydroxy propyl or mixed base thereof,, R ² is C ₅ -C ₃₁ hydrocarbon group, Z is is a polyhydroxy hydrocarbon groups or their alkoxylated derivatives having at least three linear hydrocarbon chain attached to the hydroxyl group is directly linear hydrocarbon chain ).

Preferably R ¹ is C ₁ -C ₄ alkyl, more preferably C ₁ alkyl or C ₂ alkyl, most preferably a methyl group, and R ² is C ₇ -C ₁₉ straight chain alkyl or alkenyl. , preferably C ₉ -C ₁₈ straight chain alkyl or alkenyl, more preferably C ₁₁ -C _{1 8} straight chain alkyl or alkenyl, most preferably C ₁₁ -C ₁₄ straight chain alkyl or alkenyl, or mixtures thereof, It is straight-chain alkyl or alkenyl. Z is preferably obtained from a reducing sugar by a reductive amination reaction. More preferably, Z is a glycityl group. Suitable reducing sugars include glucose, fructose, maltose,
Lactose, galactose, mannose, and xylose. High dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be used as raw materials, as well as the individual sugars listed above.
These corn syrups can produce a mixture of sugar components for Z. It should be understood that this is not meant to mean excluding other suitable raw materials. Z _{is, -CH 2 - (CHOH) n} -CH 2 OH, -CH (CH 2 OH) - (CH
OH) _n-1 -CH ₂ OH, -CH _2- (CHOH) ₂ (CHOR ') (CHOH) -CH ₂ O
H. In the formula of Z, n is an integer of 3 to 5, and R ′
Is H or a cyclic or aliphatic monosaccharide and alkoxylated derivatives thereof. Glycityl wherein n is 4, especially CH ₂ — (CHOH) ₄ —CH ₂ OH, is most preferred.

In the above general formula: R ² —C (O) —N (R ¹ ) —Z, R ¹ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, It can be N-2-hydroxyethyl, or N-2-hydroxypropyl. R ² −
C (O) -N <is, for example, cocamide, stearamide, oleamide, lauramide,
It can be myristamide, capricamide, palmitamide, tallowwamide, and the like. Z is 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymannityl, 1-deoxymaltotriotyl and the like. be able to.

Suitable polyhydroxy fatty acid amide surfactants for use in the present invention are commercially available from Hoechst under the trade name HOE®.

[0079] The preparation of polyhydroxy fatty acid amide surfactants is well known in the art. Generally, polyhydroxy fatty acid amide surfactants react an alkylamine with a reducing sugar by a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamine, and then convert the resulting N-alkyl polyhydroxyamine to a fatty acid fatty acid. It can be produced by reacting with an aliphatic alcohol ester or a fatty acid triglyceride in a condensation / amidation step to produce an N-alkyl N-polyhydroxy fatty acid amide product. The preparation of the polyhydroxyfatty acid amide-containing composition is described, for example, in British Patent 809,060 [Thomas Hedley & Co. Ltd.
), Issued February 18, 1959], U.S. Pat. No. 2,965,576 [E.A.
ERWilson, issued December 20, 1960], US Patent No. 2
, 703,798 [Anthony M. Schwartz,
Published March 8, 1955], US Patent No. 1,985,424 [Piggot
t), issued December 25, 1934] and International Patent Application WO 92/06070, each of which is incorporated herein by reference.

[0080] Zwitterionic betaine surfactants suitable for use in the present invention include both cationic hydrophilic groups, ie, quaternary ammonium groups and anionic hydrophilic groups, which are relatively broad in the same molecule. Contains over a range of pH. Representative anionic hydrophilic groups are
Carboxylate and sulfonate groups. However, other groups such as sulfate, phosphonate groups and the like can also be used. The general formula of the zwitterionic betaine surfactant used in the present invention is represented by the following formula:

[0081]

Embedded image ^{_{R 1 -N + (R 2)}} (R 3) R 4 X -

[0082] (wherein, R ₁ is a hydrophobic group, R ₂ represents a hydrogen atom, C ₁ -C ₆ alkyl, hydroxyalkyl or other substituted C ₁ -C ₆ alkyl group, R ₃ is C ₁ - A C ₆ alkyl, hydroxyalkyl or other substituted C ₁ -C ₆ alkyl group, wherein R ₃ may be combined with N with an R ₂ group to form a ring structure, or a C ₁ -C ₆ sulfonate R ₄ is a group for linking a cationic nitrogen atom to a hydrophilic group described later, and usually 1 to 1
An alkylene group, a hydroxyalkylene group or a polyalkoxy group containing 0 carbon atoms, and X is a hydrophilic group, usually a carboxylate or sulfonate group).

A preferred hydrophobic group R ₁ is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted, hydrocarbon chain, wherein the hydrocarbon chain is a linking group such as an amide group, an ester And the like. More preferably, R ₁ is an alkyl group containing 1 to 24, preferably 8 to 18, more preferably 10 to 16 carbon atoms. These simple alkyl groups are preferred for cost and stability reasons. However, the hydrophobic group R ₁ can also be an amide group of the formula: R _a —C (O) —NH— (C (R _b ) ₂ ) _m (where R _a is An aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted, hydrocarbon chain, preferably containing up to 8 to 20 carbon atoms, preferably up to 18 alkyl groups. An alkyl group containing carbon atoms, more preferably an alkyl group containing up to 16 carbon atoms, R _b is selected from the group consisting of hydrogen atoms and hydroxy groups, and m is 1-4, preferably 2-3, more preferably 3, no more than one hydroxy group in any (C (R _b ) ₂ ) group

Preferred R ₂ is a hydrogen atom or a C ₁ -C ₃ alkyl group, more preferably a methyl group. Preferred R ₃ is a C ₁ -C ₄ sulfonate group or a C ₁ -C ₃ alkyl group, more preferably a methyl group. Preferred R ₄ is (CH ₂ ) _n , where n is an integer from 1 to 10, preferably 1 to 6, more preferably 1 to 3.

Some commonly known examples of betaine / sulfobetaine are described in US Pat.
Nos. 82,275, 2,702,279 and 2,255,082, each of which is incorporated herein by reference.

Examples of particularly suitable alkyl dimethyl betaines include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-
N, N-dimethylammonium) acetate, 2- (N-coco-N, N-dimethylammonio) acetate, myristyldimethylbetaine, palmityldimethylbetaine, cetyldimethylbetaine, and stearyldimethylbetaine.
For example, coconut-dimethyl betaine is available from Seppic, Inc. as Amonyl (
Amonyl) is commercially available under the trade name 265®, and lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB / L® Available.

Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine, or C ₁₀ -C ₁₄ fatty acid acylamidopropylene (hydropropylene)
There is sulfobetaine. For example, C ₁₀ -C ₁₄ fatty acid acylamide propylene (hydropropylene) sulfobetaine is commercially available from Sherex Co. under the trade name “Varion CAS® Sulfobetaine”. .

[0088] Further examples of betaine, lauryl - imino - in dipropionate, Rhone - Poulenc commercially under the trade name (Rhone-Poulenc) from Miratain _{H 2 C-HA (Mirataine H} 2 C-HA) ( R) Available at

Suitable anionic surfactants for use in the compositions of the present invention include those of the general formula ROSO ₃
Water-soluble salts or acids represented by M, wherein R is hydroxy preferably with C ₁₀ -C ₂₄ hydrocarbon group, preferably a C ₁₀ -C ₂₀ alkyl or C ₁₀ -C ₂₀ alkyl component M is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium) or an ammonium or substituted ammonium cation (eg, methyl-, dimethyl), an alkyl group, more preferably a C ₁₂ -C ₁₈ alkyl group or a hydroxyalkyl group. -And trimethyl-substituted ammonium cations) and quaternary ammonium cations (such as tetramethylammonium cation and dimethylpiperidinium cation), and quaternaries derived from alkylamines (such as ethylamine, diethylamine, triethylamine and mixtures thereof). Ammonium cation. Usually, C ₁₂ -C ₁₆ alkyl chains are preferred for low temperature washing (e.g., less than 50 ℃), C ₁₆ -C ₁₈ alkyl chains are preferred for higher washing temperatures (e.g. 50 ° C. or higher).

Other anionic surfactants suitable for use in the present invention include those of the general formula RO (A)_m
SO_ThreeA water-soluble salt or acid represented by M, wherein R is C_Ten-C_{twenty four}Alkyl component
Unsubstituted C with_Ten-C_{twenty four}An alkyl or hydroxyalkyl group, preferably C₁₂ -C₂₀An alkyl or hydroxyalkyl group, more preferably C₁₂-C₁₈Archi
A is an ethoxy or propoxy unit.
, M is a number greater than zero, usually from 0.5 to 6, more preferably from 0.5 to 3.
And M is H or a cation, such as a metal cation (eg, sodium, potassium
, Lithium, calcium, magnesium etc.) or ammonium cations
Alternatively, it can be a substituted ammonium cation. Alkyl ethoxylated sulfur
Acid salts as well as alkylpropoxylated sulfates are also contemplated for use in the present invention.
Specific examples of substituted ammonium cations include methyl-, dimethyl-, trime
Tyl-ammonium cations and quaternary ammonium cations (e.g.
Tyl ammonium and dimethyl piperidinium cations), and
Lucanolamine (eg, ethyl (ethanol) amine, diethyl (diethanol)
A) amine, triethyl (triethanol) amine and mixtures thereof)
Is a cation derived from Typical examples of this type of anionic surfactant include
, C₁₂-C₁₈Alkyl polyethoxylate (1.0) sulfate [C₁₂-C₁₈E (1
. 0) SM], C₁₂-C₁₈Alkyl polyethoxylate (2.25) sulfate [C ₁₂ -C₁₈E (2.25) SM], C₁₂-C₁₈Alkyl polyethoxylate (3.
0) Sulfate [C₁₂-C₁₈E (3.0) SM], and C₁₂-C₁₈Alkyl polye
Toxylate (4.0) sulfate [C₁₂-C₁₈E (4.0) SM] and M is stool
Expediently selected from sodium and potassium.

[0091] Other anionic surfactants suitable for use in the present invention include sulfonated anionic surfactants, and suitable sulfonated anionic surfactants for use in the present invention include alkyl sulfones. salts, alkylaryl sulfonate, naphthalene sulfonate, alkyl alkoxylated sulphonates, C ₆ -C ₂₀ alkyl alkoxylated linear or branched diphenyl oxide disulfonates or mixtures thereof.

Alkyl sulfonates suitable for use in the present invention include those of the general formula RSO ₃
A water-soluble salt or acid represented by M, wherein R is a C ₆ -C ₂₀ linear or branched, saturated or unsaturated alkyl group, preferably a C ₈ -C ₁₈ alkyl group; More preferably a C ₁₄ -C ₁₇ alkyl group, 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-substituted ammonium) cation. And quaternary ammonium cations (eg, tetramethylammonium cation and dimethylpiperidinium cation), and quaternary ammonium cations derived from alkylamines (eg, ethylamine, diethylamine, triethylamine, and mixtures thereof).

Suitable alkylaryl sulfonates for use in the present invention are water-soluble salts or acids of the general formula RSO ₃ M, wherein R is an aryl group, preferably a benzyl group An aryl group substituted by a C ₆ -C ₂₀ linear or branched, saturated or unsaturated alkyl group, preferably a C ₈ -C ₁₈ alkyl group, more preferably a C ₁₀ -C ₁₆ alkyl group Or a benzyl group, where M is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.) or ammonium or substituted ammonium (eg, methyl-,
Dimethyl-, and trimethyl-substituted ammonium) and quaternary ammonium cations (eg, tetramethylammonium cation and dimethylpiperidinium cation), and quaternaries derived from alkylamines (eg, ethylamine, diethylamine, triethylamine and mixtures thereof). Ammonium cation.

Particularly suitable linear (or linear) alkyl sulfonates include C ₁₄ -C ₁₇ paraffin sulfonates, such as Hostapult available from Hoechst.
ur) (registered trademark) SAS. An example of a commercially available alkylaryl sulfonate is lauryl aryl sulfonate from Su. Ma. A particularly suitable alkyl aryl sulfonate is the alkyl benzene sulfonate commercially available from Albright & Wilson under the trade name Nansa®.

The “linear (or linear) alkyl sulfonate” refers to a group having 6 to 20 alkyl chains.
Unsubstituted alkyl sulphonates containing carbon atoms, preferably from 8 to 18, more preferably from 14 to 17 carbon atoms and wherein the alkyl chain is sulfonated at one end Means herein.

Suitable alkoxylated sulfonate surfactants for use in the present invention are represented by the general formula R (A) _m SO ₃ M, where R is an unsubstituted C ₆ -C ₂₀ alkyl group, straight-chain or branched C ₆ -C ₂₀ alkyl component hydroxyalkyl group or alkylaryl group having, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl group, C ₁₂ -C ₁₈ alkyl and more preferably A group or hydroxyalkyl group, A is an ethoxy, propoxy or butoxy unit, m is a number greater than zero,
Usually 0.5 to 6, more preferably 0.5 to 3, and M is H or a cation, such as a metal cation (such as sodium, potassium, lithium, calcium, magnesium, etc.) or an ammonium cation or a substituted ammonium cation. . Alkyl ethoxylated sulfonates, alkyl butoxylated sulfonates as well as alkyl propoxylated sulfonates are also contemplated by the present invention. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl-ammonium cations, and quaternary ammonium cations (eg, tetramethylammonium cation, dimethylpiperidinium cation), and alkanolamines (eg, ethyl (ethanol) There are cations derived from amines, such as amine, diethyl (diethanol) amine, triethyl (triethanol) amine and mixtures thereof. Examples of suitable surfactants include C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfonate [C ₁₂ -C ₁₈ E (1.0) SO ₃ M], C ₁₂
-C ₁₈ alkyl polyethoxylate (2.25) sulfonate [C ₁₂ -C ₁₈ E (
2.25) SO ₃ M], C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfonate [C ₁₂ -C ₁₈ E (3.0) SO ₃ M], and C ₁₂ -C ₁₈ alkyl There is polyethoxylate (4.0) sulphonate _{[C 12 -C 18 E (4.0} ) SO 3 M], M is conveniently selected from sodium and potassium. Particularly suitable alkoxylated sulfonates include alkylaryl polyether sulfonates commercially available from Union Carbide, such as Triton X
) -200 (registered trademark).

Suitable C ₆ -C ₂₀ alkyl alkoxylated linear or branched diphenyl oxide disulfonate surfactants for use in the present invention are represented by the following formula:

[0098]

Embedded image

In the above formula, R is C₆-C₂₀Linear or branched, saturated or unsaturated alkyl group
, Preferably C₁₂-C₁₈An alkyl group, more preferably C₁₄-C₁₆An alkyl group, X ⁺ Is H or a cation, such as an alkali metal cation (eg, sodium, potassium
, Lithium, calcium, magnesium, etc.). Used in the present invention
C which is particularly suitable for₆-C₂₀Alkyl alkoxylated linear or branched diphenyl
The oxide disulfonate surfactant is C₁₂Branched diphenyl oxide diss
Rufonic acid and C₁₆Linear diphenyl oxide disulfonic acid sodium salt
Dowfax 2A1 (Dowfax 2A1) (registered trademark)
) And Dowfax 8390®
I can do it.

Other anionic surfactants useful for detergents can also be used in the present invention. These include soap salts (including, for example, sodium, potassium, ammonium) and substituted ammonium salts of the soaps (eg, mono-, di- and tri-ethanolamine salts); for example, GB 1,082,179. disclosed the alkaline earth sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of a metal salt of citric acid; C ₈ -C ₂₄ alkyl polyglycol ether sulfate (contain ethylene oxide to 10 moles) ; alkyl ester sulfonates, for example C ₁₄ -
C ₁₆ methyl ester sulfonates; acyl glycerol sulfonates; fatty acid oleyl glycerol sulfates; alkyl phenol ethylene oxide ether sulfates; alkyl phosphates; isethionates such as acyl isethionates; N-acyl taurine salts; sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters)
Sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides (nonionic, non-sulfated compounds are described below); branched or primary alkyl sulfates;
Alkyl polyethoxycarboxylates, for example of the general formula RO (CH ₂ CH ₂ O) _k C
An alkyl polyethoxycarboxylate represented by H ₂ COO ⁻ M ⁺ (in the above formula,
R is a C ₈ -C ₂₂ alkyl group, k is an integer of 0, M may be soluble salt-forming cation). Resin acids and hydrogenated resin acids are, for example, also present in rosin, hydrogenated rosin and tall oil, or resin acids or hydrogenated resin acids derived from tall oil are also suitable. A further example is "Surfactants and Detergents (Surface
Active Agents and Detergents] ", Volumes I and II, Ed. Schwartz, Perry and Berch. A variety of such surfactants are also described in U.S. Patent No. 3,929. No. 678, Laughlin et al., Issued Dec. 30, 1975, column 23, line 58 to column 29, line 23, which are incorporated herein by reference. I have.

Other anionic surfactants suitable for use in the present invention are the acyl sarcosinates in acid and / or salt form or mixtures thereof, preferably represented by the general formula: Is a long chain acyl sarcosinate:

[0102]

Embedded image

In the above formula, M is a hydrogen atom or a cationic group, and R is an alkyl group having 11 to 15 carbon atoms, preferably 11 to 13 carbon atoms. Preferred M is a hydrogen atom or an alkali metal ion, especially a sodium or potassium ion.
This acyl sarcosinate surfactant can be obtained from sarcosine (N-methylglycine) which is a natural fatty acid and amino acid. They are suitable for use as aqueous solutions of the salts or as powders in their acid form. Since acyl sarcosinates are derivatives of natural fatty acids, they are rapidly and completely biodegradable and have good skin compatibility.

Accordingly, suitable long chain acyl sarcosinates for use in the present invention include C ₁₂ An acyl sarcosinate (ie, M is a hydrogen atom and R is 11 carbon atoms)
An acyl sarcosinate according to the above formula which is an alkyl group) and C₁₄Acyl sarco
Sinate (ie, M is a hydrogen atom and R is an alkyl group of 13 carbon atoms)
Acyl sarcosinate according to the above formula). C₁₂Acyl sarcosine
Can be obtained, for example, from Hampshire by Hamposil L-30 (Hampshire).
amposyl L-30) (commercially available). Also C₁₄Acyl sarco
Sinates are available, for example, from Hamposyl M-30 (Hamposyl M-30).
 M-30) (commercially available).

Suitable amphoteric surfactants for use in the present invention include those of the formula:₁R_TwoR_ThreeTable with NO
There are amine oxides that are used. In the above formula, R_1,R_TwoAnd R_ThreeEach independently
Saturated, substituted or unsubstituted, straight-chain (or linear) of 1 to 30 carbon atoms
Or a branched hydrocarbon chain. Amine oxide fields suitable for use in the present invention
The surfactant has the formula: R₁R_TwoR_ThreeAn amine oxide represented by NO, wherein R₁ Has 1 to 30 carbon atoms, preferably 6 to 20, more preferably 8 to 16, most preferably
Preferably a hydrocarbon chain of 8 to 12 carbon atoms,_TwoAnd R_ThreeAre independently 1 to
Substituted or unsubstituted, straight-chained of 4 carbon atoms, preferably 1 to 3 carbon atoms
(Or linear) or branched hydrocarbon chains, preferably methyl groups. R ₁ Is a saturated or unsubstituted, linear (or linear) or branched hydrocarbon
Can be a chain. Amine oxides suitable for use in the present invention include, for example,
C, commercially available from Hoechst₈-C_TenNatural blends of amine oxides
Goods and C₈-C₁₆It is a natural blend of amine oxides.

Chelating Agents The compositions of the present invention can include a chelating agent as a suitable optional ingredient. Suitable chelators can be any of those known to those skilled in the art, such as phosphonate chelators, aminocarboxylate chelators, other carboxylate chelators, polyfunctional-substituted aromatic chelators, ethylenediamine N , N'-disuccinic acid or a mixture thereof.

[0107] Chelating agents are desirable in the compositions of the present invention because they can increase the ionic strength of the compositions of the present invention and thus enhance the soil removal and bleaching performance of the compositions on various surfaces. The presence of a chelating agent can contribute to reducing loss of fabric tensile strength and / or color damage, especially during laundering with a full laundering application. In fact, chelating agents inactivate metal ions present on the surface of the fabric and / or in the cleaning composition (undiluted or diluent). If these metal ions are not passivated, they will cause radical decomposition of the peroxygen bleach.

Suitable phosphonate chelating agents for use in the present invention include ethane 1-hydroxydiphosphonic acid alkali metal salt (HEDP); alkylene poly (alkylene phosphonate), and aminoaminotri (methylene phosphonic acid) (ATMP
), Nitrilotrimethylene phosphonate (NTP), ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate (
DTPMP) and other aminophosphonate compounds. These phosphonate compounds can exist in their acid form or in the form of salts of different cationic forms on some or all of their acid functions. Suitable phosphonate chelators for use in the present invention are diethylene triamine pentamethylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP), such phosphonate chelators include:
It is commercially available from Monsanto under the trade name DEQUEST®.

[0109] Polyfunctional-substituted aromatic chelators are also useful in the compositions of the present invention. 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-
Dihydroxydisulfobenzene, such as 3,5-disulfobenzene.

Suitable biodegradable chelators for use in the present invention are ethylenediamine-N,
N'-disuccinic acid or its alkali metal salt or alkaline earth metal salt, ammonium salt or substituted ammonium salt, or a mixture thereof. Ethylenediamine-N, N-disuccinic acid, especially its (S, S) isomer, is disclosed in US Pat.
No. 704,233 [Hartman and Perkins, 1
Published November 3, 987]. Ethylenediamine-N, N
'-Disuccinic acid is available, for example, from Palmer Research Laboratories.
rch Laboratories) under the trade name ssEDDS®.

Aminocarboxylates suitable for use in the present invention include ethylenediaminetetraacetate, diethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Ethylene tetraamine hexaacetate, ethanol diglycine,
Propylenediaminetetraacetic acid (PDTA) and methylglycinedi-acetic acid (M
GDA), including the respective acid form or the respective alkali metal salt, ammonium and substituted ammonium salt forms. Particularly suitable aminocarboxylates for use in the present invention are diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid (PDTA) (for example, Trilon FS from BASF)
(Registered trademark)) and methylglycinediacetic acid (MG
DA).

Additional carboxylate chelators that can be used in the present invention include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid, or mixed acids thereof.

[0113] Still other chelating agents that can be used in the present invention are represented by the following formula:

[0114]

Embedded image

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ independently represent —H, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a —Cl, —Br, a —NO ₂ group, -C (O) R
'Is selected from the group and the group consisting of -SO ₂ R "group, wherein R' is -H, -OH group,
R ″ is selected from the group consisting of an alkyl group, an alkoxy group, an aryl group and an aryloxy group, and R ₅ , R ₆ , R ₇ and R ₈ is selected from the group consisting of -H and alkyl groups independently.

Particularly suitable chelating agents for use in the present invention are aminoaminotri (methylenephosphonic acid), diethylenetriaminopentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamine-N, N'- Disuccinic acid and mixtures thereof.

In general, the compositions according to the invention comprise up to 5% by weight of the total composition, preferably 0.01%
１．５1.5% by weight, more preferably 0.01-0.5% by weight of chelating agent.

Solvents The compositions according to the invention can furthermore comprise a solvent or a mixture of solvents. Suitable solvents in the present invention are hydrophobic solvents, hydrophilic solvents and mixed solvents thereof.

The following hydrophilicity index (HI) is used to define the hydrophilic or hydrophobic properties of the solvents used in the present invention:

[0120]

(Equation 1)

The “hydrophilic part” of a given solvent means here all of the O, CO and OH groups of a given solvent. By "molecular weight of the hydrophilic portion of the solvent" is meant herein the total molecular weight of all the hydrophilic portions of a given solvent.

The hydrophilic solvent used in the present invention has a hydrophilicity index of 18 or more, preferably 25 or more.
More preferably, it has a hydrophilicity index of 30 or more, and the hydrophobic solvent used in the present invention is 18 or more.
It has a hydrophilicity index of less than 17, preferably less than 17, more preferably 16 or less.

Hydrophobic solvents suitable for use in the present invention include paraffins, terpenes or terpene derivatives, and alkoxylated aliphatic or aromatic alcohols, aliphatic or aromatic alcohols, glycols or alkoxylated glycols and the like. There are mixed solvents. The hydrophilicity index of all these solvents is less than 18.

Suitable terpenes (having a hydrophilicity index of 0) are the mono-cyclic and bi-cyclic monoterpenes, in particular the terpenes of the hydrocarbon class including terpinenes, terpinolene, limonene and pinene, and mixtures thereof. d-Limonene, dipentene, α-pinene and / or β-pinene are highly suitable substances of this type. For example, Pinnen, SCM Glidco [SCM Glidco, Jacksonville, Florida, USA
acksonville)], commercially available under the trade name Alpha Pinene P & F].

[0125] Terpene derivatives such as alcohols, aldehydes, esters and ketones, each having a hydrophilicity index less than 18, can also be used in the present invention. Such materials are commercially available, for example, as the alpha and beta isomers of terpineol and linalool.

All types of paraffins having 2 to 20 carbon atoms, preferably 4 to 10, more preferably 6 to 8 carbon atoms, and are both linear or branched (Hydrophilicity index 0) can be used in the present invention. Octane is preferred in the present invention. Octane is commercially available, for example, from BASF.

[0127] Suitable hydrophobic alkoxylated aliphatic or aromatic alcohols for use in the present invention are of the formula R- (A) _n -OH, wherein R is 1 to 20 carbon atoms, preferably Two
A linear or branched, saturated or unsaturated, alkyl or alkyl-substituted or unsubstituted aryl group of 15, more preferably 2 to 10 carbon atoms, respectively, wherein A is alkoxy Groups, preferably butoxy, propoxy and / or ethoxy groups, wherein n is an integer from 1 to 5, preferably from 1 to 2. A suitable hydrophobic alkoxylated alcohol for use in the present invention is 1-methoxy-11-dodecanol (HI = 15).

Hydrophobic aliphatic or aromatic alcohols suitable for use in the present invention are of the formula R-
OH (where R is 1-20 carbon atoms, preferably 2-15, more preferably 2
A linear or branched, saturated or unsaturated alkyl group or an alkyl-substituted aryl group or an alkyl-unsubstituted aryl group having 10 to 10 carbon atoms. A suitable aliphatic alcohol for use in the present invention is a linear alcohol such as decanol (HI = 7). A suitable aromatic alcohol for use in the present invention is benzyl alcohol (HI = 16).

Suitable hydrophobic glycols for use in the present invention are of the formula HO—CR ₁ R ₂ —OH (
Wherein R ₁ and R ₂ are independently H or a saturated or unsaturated aliphatic and / or cyclic hydrocarbon chain of C _{2 to} C ₁₀ ). A suitable glycol for use in the present invention is dodecane glycol (HI = 16).

[0130] Hydrophobic alkoxylated glycols suitable for use in the present invention are of the formula R- (A) _n -R₁-OH (wherein R is H or OH, 1 to 20 carbon atoms, preferably 2 to
A linear, saturated or unsaturated alkyl group of 15 carbon atoms, more preferably 2 to 10 carbon atoms.
In the alkyl group, R₁Is H or 1-20 carbon atoms, preferably 2-15, more
A linear, saturated or unsaturated alkyl group, preferably of 2 to 10 carbon atoms,
A represents an alkoxy group, preferably an ethoxy group, a methoxy group and / or a propoxy group.
Wherein n is 1-5, preferably 1-2. For use in the present invention
A suitable alkoxylated glycol is methoxyoctadecanol (HI = 11)
It is.

Particularly suitable hydrophobic solvents for use in the present invention include d-limonene, dipentene, α-pinene, β-pinene, octane, benzyl alcohol, or mixtures thereof.

Suitable hydrophilic solvents for use in the present invention include alkoxylated aliphatic or aromatic alcohols, aliphatic or aromatic alcohols, glycols or alkoxylated glycols and mixtures thereof. All these solvents have a hydrophilicity index of 18 or higher.

Suitable hydrophilic alkoxylated aliphatic or aromatic alcohols for use in the present invention are of the formula R— (A) _n —OH, where R is 1 to 20 carbon atoms, preferably Two
A linear or branched, saturated or unsaturated alkyl, or alkyl-substituted or unsubstituted aryl group of 15, more preferably 2 to 10 carbon atoms, wherein A is an alkoxy group, preferably Represents a butoxy group, a propoxy group and / or
Or an ethoxy group, and n is an integer of 1 to 5, preferably 1 or 2. Particularly suitable alkoxylated alcohols for use in the present invention include methoxypropanol (HI = 37), ethoxypropanol (HI = 32), propoxypropanol (HI = 28) and / or butoxypropanol (HI =
27).

Suitable hydrophilic aliphatic or aromatic alcohols for use in the present invention are of the formula R-
OH (where R is 1-20 carbon atoms, preferably 2-15, more preferably 2
A linear or branched, saturated or unsaturated alkyl group of 10 to 10 carbon atoms,
Or an alkyl-substituted aryl group or an alkyl-unsubstituted aryl group). Aliphatic alcohols particularly suitable for use in the present invention include linear alcohols, such as ethanol (HI = 37) and / or propanol (HI = 28).
).

A suitable hydrophilic glycol for use in the present invention is of the formula HO—CR ₁ R ₂ —OH (
Wherein R ₁ and R ₂ are independently H or a saturated or unsaturated aliphatic and / or cyclic hydrocarbon chain of C _{2 to} C ₁₀ ). A particularly suitable glycol for use in the present invention is propanediol (HI = 45).

Suitable hydrophilic alkoxylated glycols for use in the present invention are of the formula R- (A) _n -R₁-OH wherein R is H or OH, or 1 to 20 carbon atoms, preferably
Is linear, saturated or unsaturated of 2 to 15, more preferably 2 to 10 carbon atoms.
A sum alkyl group, R₁Is H or 1-20 carbon atoms, preferably 2-15
More preferably a linear, saturated or unsaturated alkyl of 2 to 10 carbon atoms
A is an alkoxy group, preferably an ethoxy group, a methoxy group and / or
In the propoxy group, n is 1 to 5, preferably 1 to 2.) Used in the present invention
Particularly suitable alkoxylated glycols for use are ethoxyethoxyethanol.
(HI = 37).

The compositions according to the invention usually comprise up to 30% by weight of the total composition, preferably 0.0%.
It may contain from 1 to 15% by weight, more preferably from 0.1 to 10% by weight, most preferably from 0.5 to 5% by weight of solvent.

In a preferred embodiment in which the composition of the present invention contains a mixture of a hydrophobic solvent and a hydrophilic solvent, the weight ratio of the hydrophobic solvent to the hydrophilic solvent is 1:20 to 1: 1, more preferably May comprise a 1:14 to 1: 2 mixture of a hydrophobic solvent and a hydrophilic solvent.

When present, the solvent contributes to the excellent soil removal performance of the compositions used in the methods described herein.

Foam Reducing System The compositions according to the present invention can further comprise a foam reducing agent or a mixture thereof. Any suds reducing agent known to those skilled in the art is suitable for use in the composition of the present invention. In a preferred embodiment, a foam reducing system comprising a fatty acid with a capped alkoxylated nonionic surfactant and / or silicone as described below is used.

In general, the composition according to the invention comprises 1 × 10 ⁻⁴ to 10% by weight of the total composition, preferably 1 × 10 ^{−3 to} 5% by weight, more preferably 1 × 10 ^{−2 to} 5%. It can contain wt% fatty acids.

In general, the composition according to the invention comprises 1 × 10 ^{−3 to} 20% by weight of the total composition, preferably 1 × 10 ⁻² to 10% by weight, more preferably 5 × 10 ^{−2 to} 5%. % By weight of the end-capped (capped) alkoxylated nonionic surfactant as defined herein.

In general, the composition according to the invention comprises 1 × 10 ^{−5 to} 5% by weight of the total composition, preferably 1%.
× 10 ^-5 to 1 wt%, more preferably may contain 1 × 10 ^-4 to 0.5 wt% silicone.

[0145] Suitable fatty acids for use in the present invention are the alkaline salts of C ₈ -C ₂₄ fatty acids. Such alkali salts include salts fully saturated with metals of fatty acids, such as sodium, potassium and / or lithium salts, and ammonium and / or alkyl ammonium salts of fatty acids, with sodium salts being preferred. Suitable fatty acids for use in the present invention have from 8 to 22 carbon atoms, preferably from 8 to 20,
More preferably, it contains from 8 to 18 carbon atoms.

Suitable fatty acids are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, natural resources such as vegetable or animal esters such as palm oil, coconut oil, soybean oil, castor oil, tallow ( Beef tallow or sheep tallow), peanut oil, whale oil and fish oil, and / or babassu coconut oil), preferably hardened oils.

For example, coconut fatty acids can be obtained from UNICHEMA by PRIF.
AC) commercially available under the trade name 5900®.

Suitable end-capped (capped) alkoxylated nonionic surfactants for use in the present invention have the formula:

[0148]

Embedded image R ₁ (O—CH ₂ —CH ₂ ) _n — (OR ₂ ) _m —OR ₃

Wherein 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 -C ₁₅ alkyl or alkenyl group, even more preferably it is a C ₁₀ -C ₁₅ alkyl group;

Wherein R ₂ is a C ₁ -C ₁₀ linear or branched alkyl group, preferably a C ₂ -C ₁₀ linear or branched alkyl group, preferably a C ₃ group. ;

Wherein R ₃ is a C ₁ -C ₁₀ alkyl or alkenyl group, preferably a C ₁ -C ₅ alkyl group, more preferably a methyl group;

And in the formula, n and m are independently in the range of 1 to 20, preferably in the range of 1 to 10,
More preferably, it is an integer in the range of 1 to 5 or a mixed number thereof.

These surfactants are available from BASF under the trade name Plurafac® and from Hoechst under the trade name Genapol® under the trade name ICI Commercially available from ICI) under the trade name Symperonic®. Preferred among the end-capped (capped) nonionic alkoxylated surfactants of the above formula are Genapol (from Hoechst)
(Registered trademark) L2.5NR [Genapol (R) L2.5NR] and a nonionic surfactant commercially available under the trade name Plurafac (R) [Plurafac (R)] from BASF.

Suitable silicones for use in the present invention include any silicone and silica-
Contains silicone mixtures. Silicones are usually represented by alkylated polysiloxane materials, whereas silica is used in the form of usually finely divided and various types of hydrophobic silica, exemplified by silica airgels and xerogels. These materials can be formulated as particles, wherein the silicone is advantageously releasably formulated in a water-soluble or water-dispersible substantially non-surfactant detergent-impermeable carrier. Alternatively, the silicone can be dissolved or dispersed in a liquid carrier and applied by spraying on one or more other ingredients.

In practice, in industry practice, the term “silicone” has become a general term encompassing various relatively high molecular weight polymers containing siloxane units and various types of hydrocarbon groups. In fact, silicone compounds are widely described in the art literature. For example, U.S. Pat. Nos. 4,076,648 and 4,021,
No. 365, No. 4,749,740, No. 4,983,316, EP No. 15
Nos. 0 872, 217 501 and 499 364. The silicone compounds disclosed in those patent documents are suitable for the present invention. In general, silicone compounds can be described as siloxanes having the following general structure:

[0156]

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In the above formula, n is 20 to 2000, and each R can be independently an alkyl group or an aryl group. Examples of such substituents are methyl, ethyl, propyl, isobutyl and phenyl. Suitable polydiorganosiloxanes have trimethylsilyl endblocking units and at 25 ° C. from 5 × 10 ⁻⁵ m ² / s to 0
. It is a polydimethylsiloxane having a viscosity of 1 m ² / sec, that is to say n having a value in the range from 40 to 1500. These polydiorganosiloxanes are preferred because of their ready availability and relatively low cost.

A preferred type of silicone compound useful in the compositions of the present invention is a mixture of an alkylated siloxane of the type described above and solid silica.

The solid silica can be fumed silica, precipitated silica, or silica prepared by a gel-forming technique. These silica particles can be made hydrophobic by directly treating the silica particles with dialkylsilyl groups and / or trialkylsilane groups on silica or by treating them with a silicone resin. Suitable silicone compounds have a particle size in the range of 10 mm to 20 mm and 50 m ² / g
There is a hydrophobic silanized silica having the above specific surface area, most preferably trimethylsilanized silica. The silicone compound used in the composition of the present invention contains 1 to 30% by weight (more preferably 2.0 to 15% by weight) of silica based on the total weight of the silicone compound, whereby 2 × 10 ⁻⁴ m ² / sec. Suitably, a silicone compound having an average viscosity in the range of １1 m ² / sec is produced. Suitable silicone compounds can have a viscosity in the range of 5 × 10 ^-3 m ² / s ~0.1m ² / s, ² × 10 ^-2 m 2 / s or 4.5 × 10 ^-2 m Silicone compounds having a viscosity of ² / sec are particularly preferred.

Silicone compounds suitable for use in the present invention are commercially available from various companies, including Rhone Poulin, Fueller and Dow Corning. Examples of the silicone compound used in the present invention are silicone DB (
® 100 and Silicone Emulsion 2-3597®, both of which are commercially available from Dow Corning.

Other silicone compounds are disclosed in US Pat. No. 3,933,672 [Bartrotor
ollota) et al.]. Other particularly useful silicone compounds are the self-emulsifying silicone compounds described in German Patent Application DTOS 2 646 126, published April 28, 1977. An example of such a compound is DC-544®, which is a siloxane-glycol copolymer, commercially available from Dow Corning.

Typical suitable silicone compounds are described in European Patent Application EP-A-573699. The compositions described herein contain a silicone / silica mixture with a fumed non-porous silica, such as Aerosil® [Aerosil®].

Radical Scavenger The compositions of the present invention can include a radical scavenger or a mixture thereof. Radical scavengers suitable for use in the present invention include the well-known substituted mono- or di-hydroxybenzenes and their analogs, alkyl-
And aryl-carboxylates and mixtures thereof. Radical scavengers suitable for use in the present invention include di-t-butylhydroxytoluene (BHT), hydroquinone, di-t-butylhydroquinone, mono-t-butylhydroquinone, t-butylhydroxyanisole, benzoic acid, Toluic acid,
Catechol, t-butylcatechol, benzylamine, 1,1,3-tris (2-
Methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl gallate, or mixtures thereof, di-t-butylhydroxytoluene is highly preferred. Radical scavengers, such as n-propyl gallate, are commercially available from Nipa Laboratories under the trade name Nipanox S1®.

The radical scavenger, if used, is present in amounts generally up to 10% by weight of the total composition, preferably in amounts ranging from 0.001 to 0.5% by weight.

The presence of a radical scavenger indicates that when the composition of the present invention is used for cleaning applications,
It can help reduce the loss of tensile strength of the fabric and / or reduce color damage.

Antioxidants The compositions according to the invention can furthermore contain antioxidants or mixtures thereof. In general, the compositions according to the invention are present in amounts of up to 10% by weight of the total composition, preferably of 0.0
02 to 5% by weight, more preferably 0.005 to 2% by weight, most preferably 0.01 to
It may contain 1% by weight of antioxidants.

Suitable antioxidants for use in the present invention include organic acids such as citric acid, ascorbic acid, tartaric acid, adipic acid and sorbic acid, or amines such as lecithin, or amino acids such as glutamine, methionine and cysteine, or Esters such as ascorbyl palmitate (ascorbyl palmitate), ascorbyl stearate (ascorbyl stearate) and triethyl citrate, or mixtures thereof. Suitable antioxidants for use in the present invention are citric acid, ascorbic acid, ascorbyl palmitate, lecithin or mixtures thereof.

Bleaching Activator As an optional ingredient, the compositions of the present invention can include a bleaching activator or mixtures thereof. By "bleach activator" is meant herein a compound that reacts with hydrogen peroxide to produce a peracid. The peracid thus formed constitutes the activated bleach. Suitable bleach activators for use in the present invention are compounds belonging to the class of esters, amides, imides or anhydrides. Examples of suitable compounds of this type are
British Patent Nos. GB 1 586 769 and GB 2 143 231 and the preparation of bleach activators into prills (particles with a particle size of shot size) are described in published European patent application EP-A-62 523. No. An example of a bleach activator compound suitable for use in the present invention is tetraacetylethylenediamine (TAED).
) Sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate,
For example, diperoxide decanoic acid as described in U.S. Pat. No. 4,818,425 and nonoxyamide peroxyadipic acid as described in U.S. Pat. No. 4,259,201, and n-nonanoyloxybenzenesulfonate (NOBS).
It is. Substituted or unsubstituted benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecanoylcaprolactam, formylcaprolactam, acetylcaprolactam, propanoylcaprolactam, butanoylcaprolactam, pentanoylcaprolactam or mixtures thereof N-acylcaprolactams selected from the group are also suitable. A detailed system of bleach activators of interest is disclosed in EP 624 154, of which a particularly preferred one is acetyltriethyl citrate (ATC). Acetyltriethyl citrate has an eco-friendly advantage since it eventually breaks down into citric acid and alcohol. In addition, acetyltriethyl citrate has good hydrolytic stability in the product on storage and is an effective bleach activator. Finally, acetyltriethyl citrate enhances the good cleaning performance of the composition of the present invention.

The composition according to the invention may comprise from 0.01 to 20% by weight of the total composition, preferably from 1 to 10%.
% Bleach activator, more preferably 3 to 7% by weight.

Hereinafter, the present invention will be further described with reference to Examples.

[0171] The components according to the composition shown in Example Table 1 on said 1 was prepared by mixing in the ratio shown in Table 1 (unless otherwise specified in weight percent).

[0172]

[Table 1]

Dobanol® 23-3 [Dobanol® 23-3] is a C ₁₂ -C ₁₃ EO3 nonionic surfactant commercially available from Shell; Dovanol® 45 -7 [Dobanol (R) 45-7] are commercially available from shell Corporation is a C ₁₄ -C ₁₅ EO 7 nonionic surfactant; Dobanol (R) 91-8 [Dobanol (R) 91 -8] is a C ₉ -C ₁₁ EO8 nonionic surfactant commercially available from Shell; Dobanol® 91-10 [Dobanol® 91-10] is commercially available from Shell. is a C ₉ -C ₁₁ EO 10 nonionic surfactant, available in manner; alkyl betaines, Rauriruji commercially available under the trade name Jenagen LAB from Hoechst (Genagen LAB) (R) Tilvetaine; hydrogen peroxide is commercially available from Ausimont; Norasol LMW-45N® is a polycarboxylate builder commercially available from Rohm and Haas Acusol 425® is a modified polycarboxylate co-builder commercially available from Rohm and Haas.

The above-described composition is dissolved in water, a conventional laundry detergent dissolved or dispersed in water, preferably DASH futur® and DASH liq.
Fabrics, preferably soiled (colored / stained) fabrics, by producing an aqueous bath containing a laundry detergent selected from the group consisting of uid) .RTM. Was processed.

All of the above liquid compositions have shown bleaching and / or soil removal effects when used in the method according to the invention for treating fabrics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 3/37 C11D 3/37 3/395 3/395 D06L 3/02 D06L 3/02 3/16 3 / 16 (81) Designated countries 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, N, CR, CU, CZ, DE, DK, DM, 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 del Duca, Valerio Italy, 80064 Massalbrense, Corso (72) Inventor Esposito, Andrea Italy, 00167 Rome, Via, Caldinale, Caprara 34 (72) Inventor Leone, Milena Italy, 21013 Gallarate, Via, Confaronie -21 F term (reference) 4H003 AC08 AD04 DA01 DA03 EB07 EB08 EB09 EB23 EB28 EB30 ED02 EE04 EE05 EE06

Claims (17)

[Claims] 1. A process for making an aqueous bath containing a liquid composition containing a peroxygen bleach, a builder, and a modified polycarboxylate co-builder, water, and a conventional laundry detergent dissolved or dispersed in the water. And then contacting the fabric with the aqueous bath. 2. The method of claim 1, wherein the builder is selected from the group consisting of citric acid, tartaric acid, monosuccinate tartaric acid, disuccinic tartaric acid, lactic acid, oxalic acid, and malic acid and mixtures thereof. 3. The method according to claim 1, wherein the composition contains up to 40% by weight of the total composition of the builder. 4. The method according to claim 1, wherein the modified polycarboxylate co-builder is a polycarboxylate having phosphono end groups. 5. The method according to claim 1, wherein the composition contains up to 40% by weight of the total composition of modified polycarboxylate co-builders. 6. The peroxygen bleach is selected from the group consisting of hydrogen peroxide, water-soluble hydrogen peroxide source material, organic or inorganic peracids, hydroperoxides, and diacyl peroxides, and mixtures thereof, The method according to any one of claims 1 to 5. 7. The method according to claim 1, wherein the peroxygen bleach is selected from the group consisting of hydrogen peroxide, diacyl peroxide and mixtures thereof. 8. The method according to claim 1, wherein the composition contains from 0.01 to 20% by weight of the total composition of peroxygen bleach. 9. The method according to claim 1, wherein the composition has a pH of up to 9. 10. The method according to claim 1, wherein the composition further comprises an acidifying agent or a mixture thereof. 11. The method according to claim 1, wherein the composition further comprises a surfactant or a mixture thereof. 12. The method according to claim 11, wherein the surfactant is a nonionic surfactant or a zwitterionic betaine surfactant or a mixed surfactant thereof. 13. The method of claim 11, wherein the surfactant is a sulfonated anionic surfactant. 14. The composition further comprising a second surfactant selected from the group consisting of a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant and a mixed surfactant thereof.
14. The method of claim 13, wherein the method comprises a surfactant. 15. The conventional laundry detergent comprises at least one surfactant.
A method according to any one of claims 1 to 14. 16. The method according to claim 1, wherein the composition further comprises a solvent or a mixture of these solvents. 17. A method of treating fabric using a builder and a modified polycarboxylate co-builder in a laundry detergent additive containing a peroxygen bleach, thereby achieving a soil removal and / or bleaching effect. Use of builders and modified polycarboxylate co-builders in bleach-containing laundry detergent additives.