PL186733B1 - Toilet cleaning compositions - 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 invention relates to a slow-release toilet cleansing block containing a surfactant, filler and other conventional ingredients, characterized in that it comprises:

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

b) 30-50 wt.% of alkylbenzene sulfonate,

c) 10-30% by weight of sodium dichlorocyanurate (NaDCCA),

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

e) 2-10% by weight of an oily liquid perfume,

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

g) up to 5 wt.% dye and / or optical brightener.

In a preferred embodiment, the bar of the invention additionally comprises a production aid selected from mineral oil, silicone oil, water-insoluble esters other than those derived from ethylenically unsaturated carboxylic monomers, polybutene and alkoxylated alcohols.

It is believed that the combined use of the above materials enables the production of bleaching cistern blocks that have a suitable use time associated with improved durability. Without wishing to limit the invention by any theory of operation, it is believed that the polymer forms a protective layer on the surface of the bar which impedes water from entering the bar and prevents the bar from rapidly decomposing.

For a better understanding of the invention, preferred details and possible technical features of the invention are described below.

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Polymers

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

The carboxyl-containing monomers can be polymerized with themselves or in combination with other ethylenically unsaturated monomers. Preferred polymers in embodiments of this invention are those that are readily available on the market. They are cross-linked polymers of acrylic acid or methacrylic acid or maleic anhydride, or copolymers of one or more of them both with each other and with other monomers. In general, polymers derived mostly or entirely from acidic monomers are preferred.

Suitable polymers include polyacrylic acid, polymaleic anhydride and copolymers of the above-mentioned with ethylene, styrene and methylvinylether.

Typical polymers are polyacrylic acid and acrylic acid / maleic acid copolymers. In practice, these polymers are introduced in acid form, but may also be introduced as salts, for example alkali metal salts such as the sodium salt. The use of a polymer salt is advantageous if it is desired to reduce dust production during formulation and block production.

The cross-linked polyacrylate polymers used in the present invention are generally described as acrylic acid polymer resins. Such materials are available from a variety of sources and include those available under the trade names CARBOPOL ™ from Goodrich Company, SOKOLAN ™ from BASF Corporation, and under the trade name POLYGEL ™ from 3V Sigma. Cross-linked polyacrylic polymers are generally described as acrylic acid polymers that are cross-linked with additional monomers to have an effective molecular weight of from one to seven million g / mole. The average weight calculated from the formula for the polymer subunit is preferably 60-120 g / mol.

Suitably the polymer is present in an amount from 1 to 5 wt%, most preferably about 2-3 wt%. Polygel DB (TM) from 3V Sigma, a Crosslinked High Molecular Polyacrylate, has been found to be a suitable material when incorporated at about 2-3 wt%.

Surfactants

The composition also includes a surfactant component which serves as a cleaning and foaming agent, but may also act synergistically with the polymer component. Typically, the surfactant comprises up to 50% by weight of the composition.

The surfactant component includes one or more surfactants.

We have found that it is possible to obtain improved foaming properties by using a surfactant system which includes primary alkyl sulfate (PAS) together with other anionic surfactants. The invention provides a toilet bar containing 1-5 wt% primary alkyl sulfate and 30-50 wt% alkyl benzene sulfonate (ABS). We have found that the use of this mixed surfactant system is advantageous because it reduces the stickiness of the bar during the manufacturing process. Bars containing 1-5% PAS show improved wear characteristics.

It is believed that the combination of a relatively small amount of PAS with a large amount of ABS helps to foam and release odor from the bar. PAS is also believed to be much more suitable for environmental reasons than the alkyl benzene sulphonate.

Suitable anionic surfactants include polyethoxylated fatty alcohols, polyethoxylated fatty acids, polyethoxylated alkylphenols, amine oxides, and ethylene oxide / propylene oxide block copolymers.

The total amount of surfactant can vary widely. In practice, the surfactant is generally 10 to 70% by weight

% Of the composition, more preferably the surfactant is from 20 to 50% by weight.

Manufacturing auxiliaries

As will be described in more detail below, extruding the cubes is a preferred method of producing them. Optionally, the cubes according to the invention additionally contain auxiliaries to assist in the extrusion process. Suitable adjuvants include oils (both mineral and silicone oils), esters (other than those derived from ethylenically unsaturated carboxylic acid monomers), and polybutene.

An alkoxylated alcohol is a particularly suitable production auxiliary. Preferably, the alkoxylated alcohol is an ethoxylated alcohol. Preferably the amount of alkoxylated alcohol is 0.75-2% by weight. Preferably the ethoxylated chain is 40-60 in length with an average length of about 50 being preferred. Suitable materials include Empilan KM 50 / KF (TM) from Albright & Wilson. Another suitable excipient is PEG monostearate. PEG 4000 Monostearate (100%) with DAC is a suitable raw material. It is believed that this auxiliary effect results in making cubes harder and easier to cut from an extruded bar.

Fillers

Typically the bars of the invention contain 0 to 50% by weight of an inert non-polymeric and / or electrolyte filler. Preferably the bars contain 5-50 wt%, more preferably 10-30% filler.

Suitable fillers include one or more urea, sodium, magnesium and calcium carbonate, sodium chloride, borax, talc, and sodium, magnesium and calcium sulfate. Preferred ionic fillers include sodium sulfate. Preferred inert non-polymeric fillers include calcium carbonate.

Typically, the total amount of filler is in the range of 10-40% by weight of the total product.

It has been found advantageous for easier formulation and to ensure complete solubility of the rinse bars to include 10-30 wt% ionic filler as the only filler present.

For mixed filler systems, the amounts preferably are 10-20% by weight of the product, ionic filler, and 10-20% by weight of the product, inert filler. It is particularly preferred to use an approximately 50:50 mixture of sodium sulfate and calcium carbonate as filler. For mixed filler systems, it is typically present in the product in an amount of 15% by weight of each calcium carbonate and sodium sulfate.

Bleaching agents

Typically the bars contain up to 50% by weight of at least sparingly water-soluble whitening agent. Typical amounts of whitening agents in the product are 2-30% by weight of the product. For the purposes of this specification, the term whitening agent is used to denote both a whitening agent and its precursor that produces the whitening agent, unless the context is otherwise specified in the context.

Suitable bleaching agents are active halogen or active oxygen bleaching agents, especially the so-called "halogen releasing agents".

Chlorine bleaching agents are preferred. Suitable water-soluble active chlorine bleaching agents for use in the invention include chlorinated cyanuric acid esters, phthalimides, p-toluenesulfonamides, azodicarbonamides, hydantoins, glycouracils, amines and melamines. The alkali metal cyanurate salts are preferred.

A particularly preferred bleaching agent is sodium dichlorocyanurate (NaDCCA). The whitening agent is usually present in an amount of 10-30% and most preferably about 25%. Oxidan DCN / WSG (TM) from Sigma has been found to be a suitable bleaching agent.

Fragrance

Preferably the bars contain 2-15% by weight of a hydrophobic oily liquid perfume. More preferably the cubes contain 2-10%, even more preferably

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3-6% by weight of perfume. Amounts of about 4% by weight of the perfume are particularly preferred. The oily perfume is typically of the type described in European Patent Application EP 167,210. It should be understood that the oily liquid perfume must be stable in the presence of a water-soluble bleaching agent with active chlorine. Suitable oily fragrances can be readily selected by testing them in combination with a water-soluble bleaching agent with active chlorine.

Examples of suitable bleach-stable perfumes are Verdeo 898, Bonanza 048 and Ponderosa 431, all from IFF, and LB 132 from Quest. Particularly preferred fragrances are Icebreaker Super Mod, Oxygen Supra Mod, Motebianco Supra and Lemonfit Supra (all TM) from Givaudan Roure. The most preferred perfume is Green Tank Harder (TM) ex Givaudan Roure.

Minority components

Minorities are usually present, but they are optional. They include coloring and / or lightening agents. These materials should be selected so as to be compatible with the bleaching agent and not to react substantially with it. We have found that a suitable colorant is "Sudangelb 150 ™" from Sandoz, as well as Colanyl Gree ™ from Hoechst and Dispers Blue ™ from BASF.

A particularly preferred colorant is P. Green (CI 74260). A suitable brightener is titanium dioxide. The amount of colorant and / or brightener is usually below 5% by weight. For colorants, the amounts are usually in the range of 0.0001-0.1% by weight.

Further enrichment of the product can be obtained by additional use of a chelating agent, sequestrant or water softening agent, such as ethylenediaminetetraacetic acid or its derivatives, nitroletriacetic acid, polyphosphate phosphonates, metasilicates, boroheptonates, ss-tylenediamine disuccinates, dipicolinic acid, 2-phosphonobutane acid. , 4-tricarboxylic or low molecular weight polymeric materials capable of inhibiting crystal growth. Further reducing agents, such as alkali metal meta-bis-sulfates, may be present to assist in reducing staining caused by metals such as iron.

An optional minor component is a foam boosting surfactant. Suitable surfactants include amine oxides.

Production

The composition according to the invention can be prepared in various ways. For example, it can be produced by a so-called "hot-melt" process involving melting the low-melting ingredients of a cube individually and then adding the other ingredients in a mixture with the non-low-melting ingredients, and then pouring the melt into the molds. More preferably, however, the compositions of the present invention are formed into the desired final shape by compression techniques, i.e. techniques involving molding a mixture of the ingredients of the composition and then squeezing the mixture into a desired shape.

A particularly preferred process is an extrusion process in which the mixture of ingredients is extruded in the form of a uniform cube or bar which is then cut into pieces of the desired size. In this case, if the compositions according to the invention are to be used as free standing cleansing toilet blocks, suitably the weight is from 30 to 150 grams. When extruding a solid composition, it is generally preferred, as previously stated, to include some lubricant component or extrusion aids.

The compositions of the invention may also be formed into final shape by tabletting techniques.

The term cube as used herein is not intended to limit the shape of a possible product. For flush cubes, the rod is cut into pieces that are short in relation to their diameter.

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The product according to the invention is used in a method of cleaning a toilet or urinal using a block of the composition according to the invention.

To better understand the invention, the following examples are provided for the purpose of illustration only.

Examples

Cubes were produced by extrusion with the compositions A, B and C shown in Table 1 below. All amounts are expressed as percentages by weight.

The following materials were used:

alkylbenzenesulfonate NANSA HS 80 / LPF [TM] ex Albright & Wilson primary alkyl sulfate EMPICOL LZ-V [TM] from alcohol from Albright & Wilson polymer Polygel DB [TM] high molecular weight, water-insoluble, partially cross-linked acrylic acid polymer from Sigma NaDCCA OXIDAN DCN / WSG [TM] from Sigma fragrance Green Tank Harder [TM] from Givaudan Roure dye P. Green CI 74260 available as Colanyl Green GG 130 [TM] from Hoechst.

Table 1

Example AND B C. alkylbenzenesulfonate 37% 37% 38% primary alkyl sulfate 2.5% 4.5% 3.5% Polygel DB 2.0% 3.0% 2.0% NaDCCA 25% 25% 25% sodium sulfate 19.8% 16.7% 17.5% fragrance 4.0% 4.0% 4.0% dye 0.02% 0.02% 0.02% water Up to 100%

All the cubes performed satisfactorily.

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Publishing Department of the UP RP. Circulation of 50 copies. Price PLN 2.00.

Claims (2)

Patent claims 1. The slow-release toilet cleanser bar containing surfactant, filler and other common ingredients, characterized by: a) 1-5% by weight of the primary alkyl sulfate, b) 30-50 wt.% of alkylbenzene sulfonate, c) 10-30% by weight of sodium dichlorocyanurate, d) 10-30% by weight of sodium sulfate, calcium carbonate or a mixture thereof, e) 2-10% by weight of an oily liquid perfume, 1) 1-5% by weight of a water-insoluble, gelling cross-linked polyacrylate, g) up to 5% by weight of a dye and / or optical brightener. 2. Cube according to claim The process of claim 1, further comprising a production auxiliary selected from mineral oil, silicone oil, water-insoluble esters other than those derived from ethylenically unsaturated carboxylic monomers, polybutene and alkoxylated alcohols. The invention relates to slow-release toilet cleansing blocks. More specifically, it relates to solid toilet cleaning compositions that can be used to introduce cleaning ingredients and / or other ingredients into a toilet or urinal flush water by placing the composition in a toilet or urinal flush. The use of solid, slow-release blocks to incorporate cleaning ingredients and / or other ingredients into rinse water of toilets or urinals is well known. Such compositions may, for example, be placed in water in a toilet flush both as a free-standing composition and as a composition contained within a container (e.g., in the form of a dispensing container that allows the components of a solid composition to be released into the aqueous solution in a more or less uniform manner. when flushing the cistern). Alternatively, the solid composition may be suspended under the rim of the toilet in a suitable reservoir to ensure non-continuous contact of the solid material with the rinse water. For simplicity, these two solutions will hereinafter be referred to as "cisterns" (reservoir cubes) and "edge cubes". Such cubes create foam, often give off a pleasant smell and can have bactericidal properties. Solid toilet cleaning compositions typically include a surfactant component, typically together with one or more fillers or fillers (e.g., inorganic salts such as sodium sulfate, sodium chloride, etc.). Typically, such compositions also include a dye, and often a dissolution retarding material. GB-1364459 and GB-1364460 disclose that the incorporation of a hydrophobic material such as wax, stearin, long chain alcohol (up to 6EO), paradichlorobenzene or ethylene glycol monostearate into the toilet block makes it possible to control the dissolution rate of the block. Patent publication EP-0167210 relates to a toilet rim block which does not contain the perfume solid para-dichlorobenzene (PDCB). The bar contains as essential ingredients an anionic surfactant (40-90% by weight) and an inert or electrolyte filler (5-55% by weight) and an oily liquid perfume (5-55% by weight). The bar may also contain non-ionic non-surfactant polymeric materials such as polyethylene glycols and minority Ingredients such as dyes, germicides, fungicides, bleaching agents, opacifying agents and the like. Patent publication EP-0073542 describes a toilet cleansing block containing a partially esterified copolymer of vinyl methyl ether and maleic anhydride. It is also known to use polymers based on ethylenically unsaturated carboxylic acid monomers, such as polyacrylates, in solid toilet cleaning compositions. Such compositions with anti-mineralization properties are disclosed in US-4,861,511. The compositions disclosed therein contain from 2% to 15% by weight of a polyacrylate with a molecular weight in the range 500-50,000. As used herein, terms referring to average molecular weight mean weight average molecular weight, unless otherwise specified. Water-soluble materials with higher molecular weights were used in WO-96/28536, which relates to a slow-release toilet cleanser bar containing a water-soluble polymer derived from one or more monomer containing an ethylenically unsaturated carboxyl group and having a higher average molecular weight than 50,000. Acrylic acid polymers with a molecular weight of about 90,000 (such as Degapas 4104N) are preferred. Delaying dissolution is especially important when a solid composition is to be formulated as a cube. These problems are exacerbated when there is a halogen releasing agent or other bleaching agent in the bar. It is clear from EP 0206725 that halogen releasing agents are, by their nature, highly reactive chemical species serving as halogenating or oxidizing agents. In practice, it has been found that halogen release agents have a tendency to react with surfactants and / or have a tendency, when wetted, to release a gas which destroys the physical uniformity of the cleaning composition, especially in the case of free-standing cubes (without containers) intended to be placed in the toilet . These processes make it difficult to formulate a block that would have the right duration of use, i.e. about 4-6 weeks, when the toilet is flushed 15 times a day. We have found that improved cistern bars can be made containing: a bleaching agent (or a precursor thereof), an oily liquid perfume and a water-insoluble polymer derived from monomers containing one or more ethylenically unsaturated carboxyl groups.