CA1285449C

CA1285449C - Laundry detergent containing carboxylate

Info

Publication number: CA1285449C
Application number: CA000508048A
Authority: CA
Inventors: Emanuel Pantelis Fakoukakis; Tjay Yong Yap; John Richard Walker
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1985-05-01
Filing date: 1986-04-30
Publication date: 1991-07-02
Anticipated expiration: 2008-07-02
Also published as: DK164115C; IE861141L; EP0201124A2; FI861819A0; DE3684809D1; EP0201124B1; GB8511089D0; GR861144B; IE58575B1; DK198586A; FI861819L; EP0201124A3; FI83232C; FI83232B; DK198586D0; DK164115B

Abstract

ABSTRACT

Laundry compositions comprise a mixture of alkoxylated phthalate ester polymers and dicarboxylate detergency builders. The polymers provide a soil release benefit on fabrics and enhance the grease removal preperties of detergent compositions built with dicarboxylate builders.

Description

CLEANING OOMPOSIT~ONS

YAP, TJAY YONG
EMANUEL P. FAKOUKAXIS
JOHN R. W~LXER

Technical Field m e subject matter of this invention relates to cleaning oompositions which contain alkyl- or alkenyl-carboxylate materials, especially alkyl- or alkenyl-suocinates, in combination with polyester soil-release agents, as performance boosting ingredients.

Background The patent literature describes the use of alkyl- and alkenyl-succinates as surfactants: US 2.283.214;
1o detergency boosters UK 1.293.753; in various liquid cleaners UK 1.528.171, US 4.277.378; builders U5 2.462.758 and the like. See also US 3.784.486.

A variety of substituted succinates and ~sulfur-succinates~ are described for various similar-uses: ~S 3.912.663, US 4.152.515 and US 3.725.286.

The use of various succinates in combination with certain detergency ingredients is also known; see EPO
79191 and EPO 70190, as well as German 32 05 791 and German 33 17 337.

Indeed, the use of carboxylate materials of various types in solid and liquid cleaners is well-known : see UK
1.514.276 for amine soap mixtures; UK 1.429.143 for zeolite/polycarboxylate mixtures: US 2.264.103 for citrate and other carboxylate plus soap mixtures; US 3.634.392 for polysaccharidic carboxylate detergency builders: US

3.898.187 for various sulfur-succinates in dishwashing detergents; and UK 1.400.898 for use with clay softeners.

Various polyTers have ~een suggested for use in detergent compositions.

There is a continuing search for improved cleaning compositions of all types, and the present invention boosts the performance of such compositions as described more fully herei-after.

It is a major advantage of the present invention that superior product performance is achieved by the proper, and heretofore unre~ognized, combination of various known carboxylate ingredients with effective soil-release polymers.

All percentages, ratios or proportions of ingredients disclosed hereinafter are by weight, unless otherwise specified.

~.28544~

SUMMARY OF THE INVENTION.

m e present invention relates to detergent compositions designed especially for laundering fabrics.
Said compositions may be formulated in liguid, solid, or granular form; the liquid form is preferred and s w h liquid-form compositions are hereinafter referred to as "heavy-duty liquids" or "HDL's~, since they are designed to remove even the ~heaviest" soil loads from fabrics when used in a conventional laundering operation.

1o m e fully-formulated laundry compositions herein comprise a conventional alkyl- or alkenyl-dicarboxylate detergency builder (typically 1 ~ - 35 ~; preferably 5 ~ -~) conventional anionic, nonionic, cationic or zwitterionic detersive surfactants (typically 1 ~ - 35 S;
preferably 5 ~ - 20 ~) and, optionally, conventional detersive adjunct and carrier materials, and are characterized in that they contain at least 0.01 %, preferably 0.075 ~ to 5 ~, most preferably 0.1 ~ to 1.5 ~, of a soil-release polymer which is an alkoxylated ester of p~hthalic acid, as described more fully, hereinafter.

In a method aspect, the invention comprises a method for laundering fabrics by agitating said fabrics in an aqueous laundering liquor, said liquor containing at least 0.05 ~ by weight of a coTposition of the foregoing type.

Laundry additive-type prod w ts which comprise a mixture of the aforesaid builder and soil-release polymer (generally, at a ratio of 100:1 to 1:100, preferably a ratio of builder to soil-release polymer of at least 5:1) are also contemplated by this invention. Such compositions are designed to be used in combination with conventional, commercial laundry detergents.

~8S449 DETAILED DESCRIPTION OF T~E INVENTICN

The essential co~ponents of the present compositions are the di-carboxylate builder and the soil release polymer.
The detersive surfactants, optional detersive adjunct ingredients, as well as the carriers, fillers, etc., are all well-known to workers in this field.

The detergent compositions herein are preferably formulated as heavy duty liquids, but may also be formulated in solid forms as flakes, chips, powders, bars or spray-dried granules.

The detergent additive compositions may be in any of the foregoing forms.

Articles which comprise the detergent compositions or the laundry additive compositions releasably-affixed to a sheet substrate or releasably-contained in a sachet or pouch in pre-measured form, suitable for use in an aqueous laundry bath, are also contemplated by this invention.

Dicarboxvlate 8uilder : m e preferred builders herein aee of the general formula R-CH(COOH)CH2lCCCH) i.e.
derivatives of succinic acid, wherein R is C10-C20 alkyl or alkenyl, preferably C12-C16~ or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.

The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.

lZ85449 Specific examples of succinate builders include:
lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred)~ 2-pentadecenyl succinate, and the like.

Soil-Release PolYmer : The soil release polymer used herein is of a very special type, and has the generic formula:
O O O O
X-(OCH2CH2)n(O-C-R -C-OR )u (O-C-R -C-O) (CH2CH20-)n~X

in which X can be any suitable capping group, with each X
being selected from the group consisting of H, and alkyl or acyl groups containing from 1 to about4 carbon atoms.
n is selected for water solubility and generally is from about 6 to about 120, preferably from about 10 to about 50. u is critical to formulation in a liquid detergent having a relatively high ionic strength. There should be very little material in which u is greater than 5.
Furthermore there should be at least 20 ~, preferably at least 40 % of material in which u ranges from 3 to 5.

m e Rl moieties are essentially 1,4-phenylene moieties. As used herein, the term ~the * moieties are essentially 1,4- p enylene moieties~ refers to compounds where the Rl moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof. Arylene and alkarylene moieties which can be partially substituted for ~.285449 1,4-phenylene include 1,3- p enylene, 1,2-phenylene,-1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene and mixtures thereof. Alkylene and alkenylene moieties which can be partially substituted include ethylene, 1,2-propylene, 1,4-butylene, l,S-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mLxtures thereof.

For the Kl moieties, the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release properties of the conçound are not adversely affected to any great extent.
Generally, the degree of partial substitution which can be tolerated will depend upon the backbone length of the conçound, i.e., longer backbones can have greater partial substitution for 1,4-phenylene ieties. Usually, compcunds where the Rl ccmprise from about 50 to 100 %
1,4-phenylene moieties (from 0 to about 50 % moieties other than 1,4-phenylene) have adequate soil release activity. For example, polyesters made according to the present invention with a 40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate soil release activity. However, b~cause st polyesters used in fiber making oomprise ethylene terephthalate units, it is usually desirable to minimize the degree of partial substitution with ieties other than 1,4-p enylene for best soil release activity.
Preferably, the Rl moieties consist entirely of (i.e., comprise 100 ~) 1,4-phenylene ~oieties, i.e. each Rl moiety is 1,4-phenylene. (Irrespective of the m~chanism of action, it is surprising that the soil release polymers do show excellent benefits on fabrics other than polyester fabrics d the ccnçositions herein are designed to clean all manner of fabrics and textiles.) ~285449 For the R moieties, suitable ethylene or substituted ethylene moieties include ethylene,---1,2-propylene, 1,2-butylene, 1,2-hexylene,3-methoxy-1,2-propylene and mixtures thereof. Prefer~Dly, the R2 ieties are essentially ethylene ieties, 1,2-propylene mDieties or mixtures thereof. Inclusion of a greater percentage of ethylene mDieties tends to improve the soil release æ tivity of the comçounds. Surprisingly, inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubility of the compounds.

For this invention, the use of i,2-propylene ieties or a similar branched equivalent is essential for incorpDration of any substantial part of the soil release conponent in the heavy duty liquid detergent compositions. Preferably, from about 75 % to about 100 %, mDre preferalDly from about 90 % to about 100 % of the R2 mDieties are 1,2-propylene moieties.

The value for each n is at least about 6, but is preferably at least about 10. The value for each n usually ranges from about 12 to abDut 113. Typically, the value for each n is in the range of from about 12 to about 43.

A preferred process for making the preferred soil release component comprises the step of extracting a polymer having a normal distribution in which a substantial pDrtion oomprises a material in which u is greater than 6 with essentially anhydrous ethanol at low temperatures, e.g. from about 10C to abDut 15C. The ethanol soluble fraction is substantially free of the longer p~lymers and is much easier to formulate into isotropic hea~y duty liquids, especially those with higher ionic strengths, e.q. mDre than ab wt 10 % of the suocinate builder.

~85449 Although the polymers wherein u is less than about 3 are essentially of no value in providing soil release effects, they seem to importantly affect the overall product performance. In particular, the grease-removal performance of oompositions containing succinate builders can be sub-optimal: whereas when soil-release polymers are present, this performance is restored to re aoceptable levels.

Detersive Surfactants - The detergent compositions of this invention will contain organic surface-active agents (~surfactants~) to provide the usual cleaning benefits associated with the use of such materials.

Detersive surfactants useful herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic t5 surfactants. Typi~l of these ~re the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin æulfonates, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, ethoxylated aloohols and ethoxylated alkyl phenDls, and the like, which are well-known from the detergency art.
! In general, ~udh detersive surfactants oontain an alkyl group in the Cg-C18 range; the anionic detersive surfactants can be uEed in the form of their scdium, potassium or triethanolammonium salts. Standard texts 2s such ~ the J MoCutcheon's Index oontain detailed listings ! of ~uch typical detersive surfact~nts. Cll-Ci4 alkyl benzene d fonates, C12-C18 paraffin-sulfonates and Cll-C18 alkyl sulfates are especially preferred in the ccmpositions of the present type.

~.X85449 Also useful herein are the water-soluble soaps, e.g-.-the com~on s~dium and potassium coconut or tallow soaps well-known in the art.

The surfactant component can comprise as little as 1 4 of the laundry detergent compositions herein, but generally the compositions will contain 5 % to 40 %, preferably 6 % to 30 %, of surfactant. Mixtures of the anionics, such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates, with Cg-Cl6 ethoxylated alcohol surfactants are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabric.

etersive Adiuncts - The compositions herein can contain other ingredients which aid in their cleaning performance. For example, it is highly preferred that the laundry conpositions herein also contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains. Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents. Ccmmercial detersive enzymes (preferably a mlxture of ~mylase and protease) are typically used at levels of O.OOl ~ to 2 ~, and higher, in the present compositions.

Mbreover, the compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Iypical ingredients include pH regulants, perfumes, dyes, bleaches, optical brighteners, soil suspending agents, hydrotropes and gel-oontrol agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach activators and the like.

In a through-the-wash laundry mode, the oompositions are typically used at a concenteation of at least 500 W m, preferably 0.10 % to 2.5 %, in an aqueous laundry bath at pH 7-11 to launder fabrics. The laundering can be carried out by agitating fabrics with the present compositions over the range from 5C to the boil, with excellent results.

rNDU9TRIAL APPLICATION

m e following examples are typical of the preferred compositions of this invention, but are not intended to limit the scope of the invention.

EXAMPLE I

A preferred HDL is as follows:

Inqeedient Percent(Wt) 2-Dodecenyl Succinate 15.00 Soil Release Polymer * 0.50 Diethylentri d ne Penta(methylenephosphonate) 0.85 CaC12 0.01 Formate (Na) 0.9 Teiethanolamhne 5.00 NaoH 5.6 E~ol 9-0 C12 Alkyl Benzene Sulfonate 10.2 Coconutalkyl Sulfate 3.38 Ethoxylated C13_15 Alcohol (E47) 11.6 Oleic Acid 3.38 Enzymes 0.15 Water d Minors to 100 Product pH 7.6 - 7.7 lZ85449 * Prepared by esterifying 1,4 phthalic acid (chloride) with 1,2-propane diol and ethoxylating the polymer with ethylene oxide. m e resulting polymer mix is fractionated in cold (15C) ethanol to provide a cold-ethanol soluble fraction having a u value predominately in the 3 to 5 range. Average ethoxylation value (n) ranges from 12-43.

** Viscosity may be modified by replacing some of the NaOH
with RaH, according to the desires of the formulator. A
stable hcmogeneous isotropic product is secured.

It has been discovered that diluting the composition of Example I with water rapidly reduces its viscosity. m is is in direct contrast with many HDL's, whose viscosity increases when water is added. m e rapid reduction in viscosity upon addition of water helps the HDL
compositions of tnis invention avoid the problem of dispenser clogging in auto~atic washing machines or other laundry detergent dispensers.

EXAMPLE II

A laundry additive product is prepared by admixing 15 gr _ of lauryl ~uccinate with 1 gram of the soil release polymer of Example I. The composition is placed in a flexible polyethylene bag which is sealed along one edge with water-soluble polyvinyl alcohol adhesive. In use, the p~uch is simply dropped into an agueous laundry liquor, together with any conventional laundry detergent, to provide additional builder and soil-release benefits, including the remcval of clay and particulate soils from cotton and polyester fabrics.

~85449 EXAMPLE III

A granular detergent composition comprises the following ingredients:

Ingredient Percent (Wt) C12 Alkyl Benzene Sulfonate 8.0 C12-C13 Alcohol Ethoxylate ~EO 6.5) 5~0 Tallow Alcohol Sulfate 3.0 Sodium Perborate (4H2O) l9.0 Mixed C12-C14 Alkenyl Succinate 20.0 0 Sodium Sulfate 40.0 NaOH/KOH to crutcher pH 10.2 Enzyme Mix * 0.25 Soil Release Polymer ** 0.75 TAED *** l.0 Water and Minors Ealance * Alcalase/Maxatase l:l (dry mix) ** Per example I ~dry mix) *** Tetraacetyl ethylenediamine (dry mix) An aqueous crutcher mix is prepared and spray-dried.
The Enzyme Mix, Soil Release Polymer and TAED bleach activator are dry-mixed with the resulting granules.

Claims

1. A laundry detergent composition comprising conventional detersive surfactants, characterized in that it contains:

i) from 1 % to 35 % by weight of an alkyl-or alkenyl-dicarboxylate detergency builder;
ii) at least 0.01 % by weight of a soil release polymer which is an alkoxylated ester of phthalic acid.

2. A composition according to Claim 1 wherein the dicarboxylate builder is a C12-C16 alkyl-or alkenyl-succinate.

3. A composition according to Claim 2 which comprises 5 %
to 20 % by weight of said succinate material as builder.

4. A composition according to Claim 1 wherein the soil release polymer is of the formula:

(CH2CH2O-)n-X

wherein R1 is 1,4-phenylene; R2 is 1,2-propylene:
X is hydrogen n is an integer of 6 to 120; u is generally an integer of 5, or less, with at least 20 %
to 40 % of the material having u ranging from 3 to 5.

5. A liquid detergent according to Claim 4.

6. A liquid detergent according to Claim 5 which comprises from 5 % to 20 % by weight of a C12-C16 alkyl-or alkenyl-succinate builder.

7. A laundry additive comprising:
a) A soil release polymer which is an alkoxylated ester of phthalic acid and b) an alkyl-or alkenyl-dicarboxylate builder, at a weight ratio of builder : soil-release polymer of 100:1 to 1:100.

8. A composition according to Claim 7 comprising the soil release polymer of Claim 4 and the builder of Claim 2, at a weight ratio of builder: polymer of at least 5:1.

9. A composition according to Claim 1 or 7 releasably-contained in a sachet or pouch, or releasably-affixed to a sheet substrate.

10. A method of laundering fabrics which comprises agi-tating fabrics in an aqueous bath containing at least 500 ppm of a composition according to Claim 1, 2 or 3.