Amphiphile polymers based on polyester with condensed acetal...

Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – Specific organic component

Reexamination Certificate

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C510S361000, C510S434000, C510S437000, C510S479000, C510S488000, C510S533000

Reexamination Certificate




1. Field of the Invention
The object of the invention in question is formed by amphiphilic polymers, which are liquid at room temperature, on the basis of polyesters with condensed acetal groups pursuant to Formula I (soil-release polymers), their use in powdery and liquid washing and cleaning agents and the use of these agents in textile processing and for washing and cleaning contaminated surfaces, in particular hard surfaces and fabric surfaces.
2. Description of the Prior Art
The composition of formulations for washing and cleaning agents is a complex task, as the formulations must be in a position to remove soiling of various natures from soiled surfaces, e.g. fabric surfaces. In particular, quick and efficient removal of fatty or oily adhesions is generally problematic.
In order to maintain natural resources, not only is the use of tensides on the basis of replenishing raw materials necessary, but also, quite particularly, the production of formulations which become more and more effective despite a constant use of raw materials, yet also fulfil the requirements made of their biological decomposition. In addition, the formulations for washing and cleaning agents containing tensides, which are becoming more and more compact, must quickly dissolve in water in view of the decreasing amount of water in the washing process used for ecological reasons.
All these requirements can no longer be fulfilled in a physical way alone, but demand the use of higher-capability formulations with new, if possible multifunctional ingredients.
The state of the art contains washing and cleaning agents containing so-called “soil-repellent” and “soil-release” polymers. Inter alia, these compounds have the effect that released soil particles do not settle on the fabric again, thus not leading to greying.
DE-A-14 69 403 describes a process for surface-amendment treatment of articles derived from polyesters. In it, the manufactured polyesters of ethylene terephthalate units (ET) are enriched with ET:POET=2-6:1, with polyethylene glycol with mol weights of 1000-4000 being used (POET=polyoxyethylene terephthalate). The coating of the fibres is done by heat treatment with the polyester at temperatures of about 90° C., through which the fabric is given a lasting surface treatment, not only resulting in a protective layer, but also preventing static charging of the fabric.
In U.S. Pat. No. 4,427,557 and EP-A 0 066 944, anionically modified polyesters are described, which contain not only ethylene terephthalate and polyoxyethylene terephthalate units, but also, as further polymerisation components, the sodium salt of sulpho-isophthal acid. The polymerised polyethylene glycols (PEG) have mol masses of 200-1000 and, following their polymerisation with ethylene glycol (EG) and terephthal acid, result in polyesters with mol weights of 2000-10000.
U.S. Pat. No. 3,959,230 claims ET/POET polyesters with ET:POET=25:75-35:65, with low-molecular polyethylene glycols with mol weights of 300-700 being used and the polyesters obtained having mol weights of 25000-55000.
Alongside the effect as a soil-release polymer, EP-A-0 319 094 also claims the use of ET/POET co-polymers as textile ancillaries for the treatment of washing in automatic dryers. Here, the benefits of anti-static properties of the washing treated with soil-release polymers is particularly emphasised.
A favourably priced version of the soil-release polymers, i.e. as a method for introducing soil-release polymers into a watery formulation or into the washing liquid, is described in U.S. Pat. No. 4,740,326 with a “coating” onto a water-impermeable carrier. Various fibre systems such as nylon or a so-called Reemay fibre act as the foundation of the plugging.
As a further version of the above mentioned polyesters, the application of branched monomer glycol modules is claimed, e.g. 1,2-propylene, 1,2-butylene and 3-methoxy-1,2-propylene glycogen (EP-A-0 241 985).
The performance of the soil-release polymers used (WO 92 06 152) can be increased in anionic or non-ionic tenside formulation by the addition of tensides on the basis of polyhydroxy fatty acid amides (glucamides).
A further modification of the polyesters contains the inclusion of cationic components on the basis of quartenary nitrogen compounds, which are claimed to be even more effective in comparison with non-ionic polyesters (U.S. Pat. No. 4,956,447).
In EP-A-0 253 567 and EP-A-0 357 280, there is particular description of capped polyesters, which are capped on the one hand by non-ionic groups such as C1- to C4-alkyl, C1- to C4-hydroxyalkyl, C1- to C4-acyl, as well as by ionic succinate groups.
The activity of a soil-release polymer in a liquid washing agent formulation as well as the storage stability of the formulation can be improved by the addition of small amounts of salt according to DE-A-34 11 941.
As a further version of soil-release polymers, DE-A-33 24 258 describes the release or dispersion of a PET/POET polyester with PET:POET=2-6:1 in a liquid, non-ionic tenside and spraying of this mixture onto a builder (PET-polyethylene terephthalate).
Through the depositing of the soil-release polymers together with alkaline washing agent components, the latter suffer losses of activity to be ascribed to a hydrolysis of the ester compounds. This can be counteracted by a fusion of PET/POET co-polymers with alkali-metal polyacrylates at 70 to 150° C. and subsequent pulverisation (U.S. Pat. No. 4,571,303, U.S. Pat. No. 4,569,772).
DE-A-37 27 727 states the use of PET obtained from waste bottles as a particular benefit in the production of PET/POET co-polymers.
DE-A-40 01 415 claims the synthesis and use of a polyester as a greying-inhibiting and soil-release additive for powdery and liquid washing agents. The polyesters are obtained by condensation of carbonic acids containing at least 2 carboxyl groups with multivalent alcohols. In addition, alkoxylated multivalent alcohols are used, which are obtained by attaching of 5-80 mol ethylene oxide (EO) and/or propylene oxide(PO). The products excel thanks to an improved effectiveness and a better compatibility with liquid and powdery washing agent formulations.
In EP-A-0 523 956, a washing agent formulation is described which contains a water-soluble or water-dispersible co-polymer containing a UV-absorbent monomer. The manufacture of this soil-release polymer is done by poly-condensation of DMT with EG, PEG (mol weight 200-3000) and methyl4-aminobenzoate (DMT=dimethyl terephthalate).
A feature of the soil-release polymers currently being claimed is their insufficient water-solubility or bad dispersibility in water. This results in such substances only partly passing into the washing water and thus having bad soil-release properties. Further, the soil-release polymers claimed up to now have a solid consistency. When they are later used in a formulation, this requires treatment, i.e. the soil-release polymer used in the reaction process must be ground, granulated or sprayed onto a carrier (e.g. sodium sulphate). Some of the soil-release polymers are also offered as an aqueous dispersion with the disadvantages of a low active content, separation of particles of solid matter during storage and the introduction of water when used in a washing agent formulation.
The invention in question is based on the task of providing new materials and washing agent additives without the impairing properties mentioned above.
The task is solved by the invention in question with subfactant polymers pursuant to the sum formula I. The object of the invention in question is therefore subfactant polyesters pursuant to the empirical sum formula I
(CAP) represents end groups which cap the polymer at the end and are
a.) sulpho-aroyl groups
b.) groups with the formula MO
—, in which M stands for a metal ion, in particular alkaline (sodium or potassium salt being particularly preferred) or ea


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