HU226080B1 - Lavatory cleansing composition and method for its use - Google Patents

Abstract

A slow-release lavatory cleansing block comprising: a) a bleaching agent or precursor therefor, b) an oily liquid perfume, and c) a water-insoluble, gelling polymer derived from one or more ethylenically unsaturated carboxyl group-containing monomers.

Description

The present invention relates to improved toilet blocking compositions. More particularly, the present invention relates to solid toilet cleaning compositions which, when placed in a toilet or urine container, deliver cleaning and / or other components to the rinse water.

Slow-release solid block formulations that deliver cleansing and / or other components to toilet or urine container flushing water are well known products. Such compositions are placed freely or in a container (i.e., a dosing container for delivering a more or less defined amount of the solid composition components) to the flushing water of the toilet tank.

The solid composition may also be placed in a suitable support structure under the rim of the toilet bowl, where it will be periodically in contact with the rinse water.

For the sake of simplicity, the two types of structure that can be used above are referred to as "flush container blocks" and "flange blocks". These block structures form a foam, often have a pleasant smell and are also germicidal.

Solid toilet cleaning block formulations typically contain a surfactant, usually one or more fillers or builders (e.g., inorganic salts such as sodium sulfate or sodium chloride). These formulations are usually coloring and often also contain a solubilizer. GB 1 364 459 and 1 364 460 disclose a toilet cleaning block which, for controlling the solubility of the components in the block, has a hydrophobic material, such as wax, stearin, long chain alcohol (containing up to 6 EO groups), parachlor, containing benzene or ethylene glycol monostearate.

EP 0 167 210 discloses a toilet block that does not contain a solid perfume component of para-dichlorobenzene (PDCB). The array contains the following materials as essential components; 40-90% by weight of anionic surfactant, 5-55% by weight of an inert or electrolytic filler and 5-55% by weight of a liquid oily perfume. The block may also contain non-surfactant nonionic polymeric materials such as polyethylene glycols and minor amounts of other additives such as dyes, germicides, fungicides, bleaches or opacifiers.

EP 0 073 542 discloses a toilet cleaning block comprising a copolymer of partially esterified vinyl methyl ether and molecular anhydride.

Polymers of ethylene-unsaturated carboxyl-containing monomers, such as polyacrylates, are known to be used in solid toilet cleaning compositions. These compositions prevent mineral salt deposition as disclosed in U.S. Patent No. 4,861,511. These compositions contain from 2 to 15% by weight of a polyacrylate having a molecular weight of 500 to 50,000. The term "molecular weight" as used herein refers to average molecular weight unless otherwise specified.

WO 96/28536 discloses a slow release toilet cleansing block comprising higher molecular weight, water soluble materials comprising one or more ethylenically unsaturated carboxyl groups and having an average molecular weight greater than 50,000. Approx. Acrylic acid polymers having an average molecular weight of 90,000 (for example, Degapas 4104N).

In the case of flushing container block structures, it is particularly important to slow the solubility. These problems occur mainly when the formulations contain a halogen releasing or other bleaching agent. It is clear from EP 0 206 725 that halogen releasing agents are inherently chemically reactive and can therefore be used as halogenating or oxidizing agents. In practice, it has been found that halogen-releasing agents tend to react with surfactants and / or that the gas formed upon wetting endangers the physical integrity of the cleaning composition. This is especially true for an open block inserted into the toilet tank. Because of this, it is difficult to have an acceptable lifetime of 15 rinses a day, approx. Preparation of arrays for 4-6 weeks.

In our work, we have discovered that compositions of the following compositions can be formulated into improved rinse container blocks using a bleaching agent (or precursor compound), a liquid oily perfume, and a water-insoluble polymer derived from one or more ethylenically unsaturated carboxylic group monomers.

SUMMARY OF THE INVENTION The present invention relates to a slow release toilet cleaning block composition having the following composition:

(a) a bleaching agent or a precursor compound;

b) liquid, oily perfume; and

c) a water-insoluble gelling polymer derived from one or more ethylenically unsaturated carboxylic monomers.

It is believed that the combination of the above materials will result in a bleaching pad for use in a rinse tank, which will have an acceptable service life due to improved stability. Without any particular theoretical discussion, it can be said that the polymer forms a protective layer on the surface of the block that prevents water from contacting the block and prevents the block from being rapidly degraded.

The following is a detailed description of the advantageous and essential features of the invention.

polymers

The water-insoluble, gelling polymers used in the composition of the present invention are polycarboxylic acids derived from one or more ethylenically unsaturated carboxyl-containing monomers, in particular ethylenically unsaturated carboxylic acids, such as acrylic acid or maleic acid.

HU 226,080 Β1

Carboxyl-containing monomers may be polymerized alone or in association with other ethylenically unsaturated monomers. Preferred polymers for the purposes of the present invention are readily commercially available materials. These materials are polymers of acrylic acid, methacrylic acid or maleic anhydride or copolymers thereof with one another or with other monomers.

Generally, polymers prepared from most or all of the acidic monomers are preferred.

Suitable polymers are polyacrylic acid, polymaleic anhydride and copolymers thereof with ethylene, styrene or methyl vinyl ether.

Typical polymers are polyacrylic acid and acrylic acid / maleic acid copolymers. These polymers may be used in practice in the form of an acid or a salt such as an alkali metal salt such as a sodium salt. If it is desirable to reduce the amount of powder formed during manufacture and molding, the use of a polymer salt is preferred.

Preferably, the polymer is cross-linked. The cross-linked polyacrylate polymers of the present invention are generally acrylic acid polymer resins. Such materials are commercially available, for example, from B.F. Goodrich Company, under the trade name CARBOPOL, under the trade name BASF Corporation under the trade name SOKOLAN, and under the trade name 3V Sigma POLYGEL. Crosslinked polyacrylate polymers are generally acrylic acid polymers which are crosslinked with additional monomer or monomers to give an effective molecular weight of 1,000,000 to 7,000,000 g / mol. The average weight of the polymeric subunit molecule is 60-120 g / mol.

The amount of polymer used is 0.5-20% by weight, more preferably 1-5% by weight, and most preferably 2-3% by weight. Crosslinked high molecular weight polyacrylate (Polygel) from 3V Sigma is preferably used in an amount of 2 to 3% by weight.

Surfactants

The composition of the invention also contains anionic or cationic surfactants. The surfactant is used for cleaning and foaming and may also show synergistic effects with the polymer component. The amount is typically up to 50% by weight of the composition.

The surfactant component comprises one or more anionic surfactants and optionally in combination with one or more nonionic surfactants. Suitable anionic surfactants include alkali metal or ammonium alkyl aryl sulfonates (especially alkyl benzene sulfonates), alkanesulfonates, alkyl sulfates and sarcosinates.

In our work, we have found that improved foam surfactant systems can be prepared from the following ingredients: a primary alkyl sulfate (PAS) and other anionic surfactants. The toilet cleaning unit according to the invention preferably contains from 1 to 15% by weight, more preferably from 1 to 5% by weight, of primary alkyl sulfate and from 15 to 50%, more preferably from 30 to 50% by weight of other anionic surfactants. In our work, it has been found that the use of such mixed surfactants is advantageous because the adhesion of the block is reduced during manufacture. The

Blocks containing 1-5% by weight PAS exhibit good abrasion resistance.

Another preferred anionic surfactant is the sulfonate surfactant. Suitable examples of such materials are alkyl benzene sulfonates (ABS). It is believed that the combination of a relatively small amount of PAS with a relatively large amount of ABS improves the foaming and perfume release of the array. PAS is also more environmentally acceptable than alkyl benzene sulfonate.

Suitable nonionic surfactants include polyethoxylated fatty alcohols, polyethoxylated fatty acids, polyethoxylated alkyl phenols, amino oxides and ethylene oxide / propylene oxide block polymers.

The amount of surfactant, if used, can be varied within wide limits. This amount is generally 10 to 70% by weight of the composition, preferably 20 to 50% by weight.

Processing aids

Preferably, the preparation is carried out by extrusion as described below. The block formulation of the present invention may optionally contain a processing aid to aid extrusion. Suitable processing aids include oils (including mineral and silicone oils), esters (other than ethylenically unsaturated carboxyl-containing monomers) and polybutene.

One particularly useful processing aid is an alkoxylated alcohol, including ethoxylated alcohol. The amount used is preferably from 0.75 to 2% by weight. Preferably, the alkoxyl chain is 40-60 in length, with an average length of about. 50. Such material is marketed, for example, under the tradename Albright and Wilson Empilan KM 50 / KF. Another useful processing aid is PEGmonostearate. Such material is marketed, for example, under the tradename DAC PEG4000 Monostearate (100%). This processing aid is expected to make the block harder and thus easier to cut from the extruder.

extender

The bulk compositions of the present invention typically contain from 0% to 50% by weight, preferably from 5% to 50% by weight, and more preferably from 10% to 30% by weight of inert non-polymeric and / or electrolyte filler.

Suitable fillers include one or more of the following materials: urea, sodium, magnesium and calcium carbonate, sodium chloride, borax, talc, sodium, magnesium and calcium sulfate. An ionic charger3 is preferred

Substances such as sodium sulfate and inert non-polymeric fillers such as calcium carbonate.

The amount of filler used is typically 10-40% by weight of the composition.

It has been found that, when a single filler is used in an amount of 10-30% by weight of an ionic filler, the composition is easy to formulate and easily soluble in flush container blocks.

In mixed filler systems, the amount of filler is 10-20% by weight of ionic filler and 10-20% by weight of inert filler, based on the weight of the product. Particularly suitable for approx. 50:50 mixture of sodium sulfate and calcium carbonate. The amount of mixed filler systems is typically 15 to 15% by weight of calcium carbonate and sodium sulfate, based on the weight of the product.

Bleachers

The block formulations of the present invention contain up to 50% by weight of at least a water-soluble bleach. Typical amounts are 2 to 30% by weight of the product. Unless otherwise specified, the term "bleaching agent" as used herein refers to bleaching agents or to the precursor compounds that are derived from them.

Active halide and active oxygen bleaching agents, in particular so-called "halogen-releasing agents", are suitable.

Chlorine-containing bleaching agents are preferred. Water-soluble active chlorine-containing bleaching agents suitable for use in the present invention include chlorinated cyanurates, phthalimides, p-toluenesulfonamides, azodicarbonamides, hydantoin, glycoluracil compounds, amines and melamines. Alkali metal salts of cyanurate are preferred.

A particularly preferred bleaching agent is sodium dichlorocyanurate (NaDCCA). Typical amounts of bleach used are from 10 to 30% by weight of the composition, preferably from about 10% to about 30% by weight. 25% by weight. Suitable bleaching agents are Oxidan DCN / WSG from Sigma.

perfumes

The block compositions of the invention are preferably

They contain from 2 to 15% by weight, preferably from 2 to 10% by weight, and more preferably from 3 to 6% by weight, of a liquid oily hydrophobic perfume. The amount of perfume is particularly preferably about 4% by weight. Such an oily perfume is disclosed in EP 167 210. It should be noted that the liquid oily perfume must be stable in the presence of a water-soluble active chlorine bleach. A suitable perfume may be selected by testing in combination with a water-soluble active chlorine-containing bleach.

Suitable perfumes are IFF (Verdeo 898, Bonanza 048 and Ponderosa 431) and Qes (LB ISZ). Givandan Roure's Icebraker Super Mode, Oxygen Supra Mode, Montebianco Supro and Lemofit Supro are particularly suitable. The most preferred perfume is Givanden Roure's Green Tank Harder.

Other additives may be used in small quantities

Small amounts of other additives may optionally be included in the compositions of the invention. These include colorants and / or white colorants. These materials should be selected so as to be compatible with the bleaching agent and not to react to a significant degree with it. Suitable coloring agents for use in the composition of the invention include Colonyl Green (Hoechst), Dispers Blue (BASF); and P. Green (Cl 74260). A well-used white colorant is titanium dioxide. The amount of dyes and / or white dyes used is typically less than 5% by weight. Typical amounts of colorants are 0.0001-0.1% by weight.

The following substances may also be used to further improve the effect of the composition of the invention: chelating agent, sequestering agent, water softening agent such as ethylenediaminetetraacetic acid or a derivative thereof, nitrilotriacetic acid, polyphosphate phosphonates, metasilicates, boron heptonates, s, s- ethylene diamine disuccinate, dipicolinic acid, 2-phosphono-butane-1,2,4-tricarboxylic acid, or low molecular weight polymeric materials which inhibit crystal growth; and alkali metal metahydrogen sulfates used to remove stains caused by metals such as iron.

A further foaming agent may be used as a minor additive optionally. Suitable surfactants include amine oxides.

process

A variety of methods can be used to prepare the compositions of the present invention. One method is, for example, the so-called "hot melt" process, in which the meltable components of the bulk composition are melted individually, and the molten materials are mixed with the non-meltable components and the mixture is poured into molds. More preferred, however, is a process wherein the compositions of the present invention are formed by compression to produce the desired product. In this process, the components of the composition are first blended and then compressed to form the desired product.

Particularly preferred is an extrusion process in which a solid roll or rod is extruded from a mixture of components and then cut into pieces of the desired size.

When used in the form of a freestanding toilet cleaning unit, the compositions of the present invention will have a suitable weight of 30 to 150 g. When a solid composition is extruded, it is generally preferable to use any lubricant or processing aid to aid in extrusion, as described above.

HU 226,080 Β1

The compositions of the present invention can also be formulated into tablets of the desired shape by tabletting.

The term "block" as used herein does not affect the actual shape of the product, in the case of rinsing tank blocks, the rod is cut to a length that is short in diameter.

Preferred compositions

Preferred embodiments of the invention include slow release toilet cleaning block compositions having the following composition:

a) 2 to 30% by weight of a halogen releasing agent;

b) 2-15% by weight liquid oily perfume; and

c) 1-5% by weight of a water-soluble, gelling polymer derived from one or more ethylenically unsaturated carboxylic monomers.

Particularly preferred compositions of the invention have the following composition:

a) 1-5% by weight of primary alkyl sulfate;

b) 30-50% by weight of alkylbenzene sulfonate;

c) 10-30 wt% NaDCCA;

d) 10-30% by weight of sodium sulfate, calcium carbonate or mixtures thereof;

e) 2-10% by weight liquid oily perfume;

f) 1-5% by weight water-insoluble, gelling cross-linked polyacrylate;

g) 0-5% by weight of coloring agent and / or optical brightener.

The present invention also relates to a toilet and urine cleaning method with the bulk composition of the invention.

The following examples illustrate the invention in more detail.

Compositions A, B, C and D of the present invention are prepared by extrusion from the ingredients described in Table 1. Quantities are given in units of weight.

The materials used are: alkylbenzenesulfonate: Albright and Wilson, NANSA HS80 / LPF;

primary alkyl sulfate: Albright and Wilson

EMPICOL LZ-V;

polymer: Polygel PB, a high molecular weight, partially crosslinked acrylic acid polymer from Sigma;

NaDCCA: OXIDAN DCN / WSG from Sigma;

perfume: Givandan Roure Green Tank Harder;

colourant: P. Green from Hoechst under the tradename Colanyl Green 25 CG130

CI7426 product.

Table 1

Example THE(%) B (%) C (%) D (%) Alkyl benzene sulfonate 37 37 38 33.5 Primary alkyl sulfonate 2.5 4.5 3.5 8.0 Polygel DB 2.0 3.0 2.0 3.0 NaDCCA 25 25 25 25 Sodium sulfate 19.8 16.7 17.5 17.2 Perfume 4.0 4.0 4.0 4.0 Coloring agent 0.02 0.02 0.02 0.02 Water 100%

All of the above block formulations have a satisfactory effect.

Claims (9)

1. A slow release toilet blocking composition having the following composition: 50 (a) a bleaching agent or a precursor compound thereof; b) liquid, oily perfume; and (c) a water-insoluble gelling polymer derived from one or more ethylenically unsaturated carboxylic monomers which are partially cross-linked below. The block formulation of claim 1, wherein the polymer is selected from the group consisting of polyacrylic acid, acrylic acid / maleic acid copolymer, and metal salts thereof. 60 A block formulation according to claim 1 or 2, comprising 0.5 to 20% by weight of polymer. 4. A block formulation according to any one of claims 1 to 5, comprising 1-5% by weight of polymer. 5. A block formulation according to any one of claims 1 to 6, further comprising a processing aid selected from the group consisting of mineral oil, silicone oil, water-insoluble ester other than ester derived from monomers containing ethylenically unsaturated carboxyl groups, polybutene and alkoxylated alcohols. 6. A block formulation according to any one of claims 1 to 5, comprising a bleaching agent selected from the group consisting of chlorinated cyanurates, phthalimides, p-toluenesulfonamides, azodicarbonamides, hydantoin, glycol lauracil derivatives, amines and melamines. 7. An array composition according to any one of claims 1 to 3, which has the following composition: HU 226,080 Β1 a) 2 to 30% by weight of a halogen releasing agent; b) 2-15% by weight liquid oily perfume; and c) 1-5% by weight of a water-soluble, gelling polymer derived from one or more ethylenically unsaturated carboxylic monomers. 5 8. An array composition according to any one of claims 1 to 3, which has the following composition: a) 1-5% by weight of primary alkyl sulfate; b) 30-50% by weight of alkylbenzenesulfonate; c) 10-30% by weight of sodium dichlorocyanurate; 10 d) 10-30% by weight of sodium sulfate, calcium carbonate or mixtures thereof; e) 2-10% by weight liquid oily perfume; f) 1-5% by weight water-insoluble, gelling cross-linked polyacrylate; g) 0-5% by weight of coloring agent and / or optical brightener. 9. A method for cleaning a toilet or urine comprising the steps of 1-8. A block composition according to any one of claims 1 to 6 is used.