FR2514026A1 - LIQUID COMPOSITION WITHOUT DANGER AND METHOD FOR CLEANING WATER-CLOSETS CUPTES - Google Patents

Abstract

THE INVENTION RELATES TO A SAFE LIQUID COMPOSITION AND TO A PROCESS FOR CLEANING WATER-CLOSET BOWLS; A THICK LIQUID CLEANER FOR WATER-CLOSET CUPS CONSISTS OF AN ORGANIC ACID, A DETERGENT AND A THICKENER CONSTITUTING A CELLULOSIC ETHER; THIS NON-CORROSIVE PRODUCT WHICH IS RELATIVELY SAFE TO HANDLE, EFFECTIVELY ELIMINATES LIMESTONE AND IRON STAINS FROM WATER-CLOSET CUVETTES.

Description

The present invention relates to a composition

  safe liquid and a method for cleaning the cu-

vases of water closets.

  In general, the invention relates to acidic detergent compositions for hard surfaces and

  especially liquid cleaning compositions not cor-

  roses which are suitable for cleaning toilet bowls

ter-closets and the like.

  The fixed accessories of water closets and bathrooms are generally made of earthenware, porcelain, enamelled steel or stainless steel and are associated with them various accessories which can be in

  metal, for example copper-plated or chrome-plated,

  tick, rubber or treated wood Typically, the cleaning agents for water closet bowls are

  relatively corrosive acidic systems that are con-

  to have sufficient chemical activity to

  break and dissolve the staining materials, and to

  sinfect the area of the bowl The most common organic stains or deposits that accumulate in the cups of water-closets and that one wishes to eliminate,

  are calcareous scale, which is an accumula-

  calcium carbonate and iron stains and

  rust which is a complex mixture of oxide and hydroxide

  In regions where the hardness of water is high, calcium ions and other alkaline earth metal ions form insoluble salts with the carbonate, phosphate or silicate anions present in

  when water stagnates and evaporates the weak solu-

  of these salts causes their deposition at the level of the water level and in other areas subject to

  alternating periods of humidity and drought.

  Fixed earthenware accessories that we

  usually found in water closets have strong-

  tend to have iron spots when the water supplying and discharging them has a high initial iron content and iron is dissolved in the water at a lower valence state from the iron pipes The problem of iron stains is particularly acute when, after the evacuation of water, a thin film of water remains

  on a faience apparatus The evaporation of this pel-

  licule leaves iron salts that pass easily to the higher valence state It is this form of iron that adheres so strongly to the device and is therefore responsible for iron tasks unpleasant to see and undesirable. The usual active ingredient in water closet cleaners is a strong mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid or a strong sulfonic acid.

  they are effective in removing calcareous scale.

  re and iron stains, these compositions for bowls

  water closets are very dangerous and

  risk for staff and areas

  turning the water closet bowl to clean

  requires the wearing of protective clothing, in particular-

  rubber gloves, and eye protection, when using this material and to ensure that the projections are wiped away immediately to avoid damaging the walls, floors, pipes and the like. In addition, care must be taken to avoid Inhalation of the vapors or dusts of these heaters noted that in some cases, the acid vapors of these cleaners have caused corrosion of the metal elements associated with the water circuit of the toilets and other apparent metals in the water.

bathrooms.

  It is an object of the invention to provide an acidic, hard surface, safe and easy to handle acidic detergent composition. Another object of the invention is to provide a thickened non-corrosive liquid cleaning composition for cleaning the water bowls. - closets and the like Another

  The object of the invention is to provide a method for eliminating

  calcareous tartar and iron spots of the waterclosets cuvettes using the new composition

  described by prolonged contact with the stained areas.

  According to the invention, it has been discovered that an effective composition for cleaning toilet bowls can be prepared using a novel nonvolatile water-soluble organic acid, a detergent and a cellulose ether thickener. to obtain a composition having a p H of between 2.2 and 3.5 This composition eliminates calcareous scale

  and iron stains without risk of corrosion or

city.

  The preferred organic acids are

  In the water closet cleaners of the invention, they are effective in redissolving inorganic deposits such as precipitated calcium carbonate, and in reducing ferric salts deposited in ferrous salts.

  In this respect, organic acids must be

  to satisfy two selection criteria First of all,

  the acid must be soluble in water.

  the aqueous solution (10%) of the acid must have

  acid sufficient to dissolve calcium carbonate.

  Table I shows the solubilities of certain acids

organic.

TABLE I

  Organic acid Solubility at 40 ° C H Glutaric acid 35.3 1.6 Adipic acid 0.6 2.8 Succinic acid 3.2 2.4 Citric acid 51.5 0.4 Fumaric acid 0.1 Acetic acid * 10, 0 2.1 Malonic acid 51.4 0.1 Tartaric acid 59.6 0.3 Phthalic acid 0.4 * Acetic acid is soluble in all proportions and the concentration of 10% has been chosen to provide

representative p H.

  Maleic acid and oxalic acid were not tested because of their own toxicity. To evaluate the removal of calcareous scale, small blocks of calcium carbonate were weighed and treated with an experimental solution. product adjusted to a p H between 2.7 and 3.0 The elimination of limescale is given by the weight loss expressed in milligrams per gram of sample. Table II

  shows the effect of various acidic solutions on the elimination

nation of limestone tartar.

TABLE II

  Organic acid Solutions Average weight loss (mg / gs in one hour Acetic acid 1.004 3 3 14.8 Adipic acid o, 0 o 6 3.0 0.7 Succinic acid 0.32 3.0 3.7 Glutaric acid 3, 50 2.9 43.9 Citric acid 5, 20 39 19.8 Malonic acid 5.10 2.8 4, O Sokalan DCS 0.50 3.0 Commercial mixture of adipic, glutaric and

  succinique, provided by BASF Aktiengesellschaft, Ludwigs-

Haven, Germany.

  Tartaric acid has not been studied because we know

  that calcium tartrate is practically insoluble.

  In the practice of the invention, it is contemplated that the water-soluble acids are the dicarboxylic acids having 3 to 8 carbon atoms, the hydroxycarboxylic acids having 2 to 6

  carbon atoms, 1 to 5 hydroxy groups and 1 to 3 groups of

  carboxy, and fatty acids having 2 or 3 carbon atoms These acids are useful because they are stable, relatively non-corrosive and effective in dissolving

limestone scale.

  Particularly preferred acids are organic dicarboxylic acids of the formula HOOC- (CH 2) n -COOH wherein N is a whole number

  from 2 to 4, ie succinic acid, gluic acid,

  taric acid and adipic acid, as well as their mixtures.

  BASF has generally suggested that its Sokalan DCS blend of succinic, glutaric and adipic acids is useful for the manufacture of a liquid acid cleaner for water closet bowls. The final pH of the organic acid-containing composition should be in the range of 2.2 to 3.5 to achieve proper scale removal. Preferred compositions have an inclusive pH.

  between 2.7 and 3.0 It has been found that 2-7% of diacids

  preferred ones are effective and all are particularly preferred.

  approximately 5% of a mixture of succinic, glutaric and adipic acids, based on the total weight of

the composition.

  The cleaning composition of the invention comprises

  also takes a detergent to wet the treated surfaces to achieve effective contact between

  stained and / or depositing areas, and the

  Active ingredients For this purpose, the detergent may be chosen from anionic, cationic, nonionic, zwitterionic and amphoteric surfactants, oxides and the like.

  amine, esters of phosphoric acid and their

  It is desirable that the detergent produce a

  certain amount of foam and surfactants are preferred.

  Nonionic actives Preferred nonionic materials include condensates of polyethylene oxide with alkylphenols and aliphatic alcohols, such as nonylphenol ethoxylated with about 12 moles of ethylene oxide or a C 12 -C alcohol. Which is ethoxylated with

  11 moles of ethylene oxide Detergent should be

  3 to 7% of the total composition.

  The thickener of the invention is an ether of

  cellulose and it is preferably methylhydroxypropyl-

  This material increases the visco-

  of the cleaning composition of the cuvettes of water-

  closets to maintain prolonged contact with the acid, in order to dissolve limestone scale and eliminate

  rust stains The effective amounts are

  it is between 0.5 and 1.2% and 1% is particularly preferred.

  Additional ingredients such as perfumes, coloring agents and preservatives can be added to the compositions of the invention. The compositions of the invention can be produced by continuous or batch processes. When a batch of water closet cleaner is prepared according to the batch process, the quantity of water corresponding to approximately the weight formula is introduced into a mixer, and the dyestuff and a preservative are added successively with vigorous stirring (without airing).

  hydrophilic thickening material so that it dissolves

  ve and gradually swells under the effect of this agita-

  The batch is then allowed to stand for 40 minutes to complete hydration of the thickener and deaeration. At this stage, the viscosity is between 50 and 800 ° C. continuing stirring of the mixture until the acid is completely dissolved. The detergent material is then added.

  desire, to carry out a preliminary mixture of the

  tergente and perfume The agitation continues for

  still a short period to ensure a homogenous

  gene We measure p H and, if necessary, we adjust it

  according to the formula, with caustic soda and / or phosphoric acid. The finished mixture is conditioned in a suitable container such as a bottle.

  flexible plastics material having a distribution system

  suitable for spraying the mixture under the rim

of the water closet bowl.

  Cleansers for toilet bowls

  of the invention can be used in a similar way.

  to those used with currently known toilet bowl cleaners Cleaning processes using existing cleaners can be

  divide into a fast process and a slow process.

  In the quick cleaning process, it is

  usual to place the toilet bowl cleaner

  closet in the bowl, to dissolve it if it is in

  powder and spread it on the surfaces to be cleaned.

  With some liquid products, it is planned to be able to spray the cleaner under the rim of the bowl of

  water-closet You can brush the bowl of water-clo

  set to completely cover stained or coated surfaces After this initial treatment, the cleaner is allowed to act while the rest of the bathroom is being cleaned (and any other part of the home that is to be cleaned ) After having

  completed these other tasks, one can brush (or rebros-

  ser) the water closet bowl and shoot the hunt for

  rinse the cleaned water-closet bowl.

  In the slow cleaning, the operations are

  if it is not only that the initial stages are

  in the evening and the final rinse the next morning,

  which allows a cleaning of longer duration.

  With the water closet cleaner of the invention, these cleaning operations are essentially used. Since the mixture is very viscous and has excellent wetting characteristics of the surfaces in the air, it is quite useless to brush the surface. water closet bowl for efficient cleaning. However, brushing has no detrimental effect on this

cleaning.

  The following examples show cleaners

  thickened for cuvettes water closets according to the invention.

1 2 3 4 5 6 7 8 9

Formaldehyde (ss) at 30%

Methylhydroxyp 4 pwl-

cellulose -

  Sokalan Dcs 3 Nonylphenol 12 EC 4 Nonylphenol 13 OB Inchrome blue 14 (1% solution) Chloropin (perfume Eau Vîscosit & (f 50 Miyenne weight loss (Mî / g) in one hour Character of the solution M 012 012 012 0,2 012 0.2 O 2 oir 2 0.85 'o o, 0 1.0, 0 4.0 1.2, 0 1.0 4 VO 4 YO 1.0 7.0 o 7.0 1.0 110.0 7.0 7.0 110 1.0 110 1.0 leo 1> 0 1.0 1.0 QS 4 'l limpid 0.3 QS

4; 9 1

  limpid 0.3 clear QS 0.3 QS, 6 fast 0.3 QS, 6 limpid 0.3 QS, 6 clear lirtpide 4.1 limpid 0.3 clear 3.3 os 0.3 QS, 6 limpid r%) Ln to -pCD rj 0% il 12 13 14 15 i 6 17 18 Formaldehyde (30% solution)

Méthylhydroxyproyl-

  Sokalan cellulose DC 53 Nonylphenol 14 EO 6 C 9-C ethoxylated alcohol 8 EO 7 Ethoxylated C alcohols, 8 EO 8 C 12-CI 5 ethoxylated alcohol 11 EO 9 C 13 -IC 5 alcohol ethoxylated 11 EO 10 Alcohol in C, -CI 1 ethoxylated 9 OE'1 Di-ethyllaurylamine oxide 30% solution) Inchrome blue (1% solution) Chloropin (perfume Water Viscosity (f 50 CP Perto of imyenne weight (mg / cd) Character of the solution

0.2 0.2 M 012 012 M 0 2 0.2 012

  1.0 o 110 1.0 110 o 1.0 1.0, 0 510 5.0 5.0 5.0 5.0, 5.0 1.0, 0 4 5 , 0 610 3.0 4.0 O 4, o 41-0 the o 0.3 QS 4, 1 liirpide the o 0.3 QS 4.1 limide the o 0.3 QS 4.1 amide lyo 0.3 QS the o 0, 3 QS the o 0.3 bone 4.1 limpid 1.0 0, 3 QS 4) 11 limpid 1.0 0, 3 bone (4.1 limpid the o 0.3 QS 4.1 limpid 4, i 4, i limpid r O tq C> NI 0%

19 20 21 22 23 24 25 26 27 28

Formaldehyde (30% solution)

Méthylhîdroxypryl-

  oel ulose Yellow to xanthan Sokalan OD 53 4, Nonylphenol 12 o E Alcohol C -C ethoxylated 8 o E 7 9

0.2 0.2

0.2 0.2

, 0 o, 85, 0 0.3

, 0 5.0

, 0 1.0, 0 0.5 0.3

, 0 7.0

0.3 0.3, 0.4, 0.3, 2.0 2.0

) 0 5.0 5.0

  Paraffin Sodium sulfonate 60% solution Phospha Organic 16 D Sodium dclecylbenzenesulfonate (sodium chloride Acetic acid NIM Na 3% solution Octylphenol EO 3017 Methyl salicylate Kathon 886 wd 13 (concentrated solutin) Inchrome blue (1: 1 solution %) Chloropin (, perfume L; 2 u Viscosity (50 CP Alcyen weight loss (mg / g) Character, solution 2.0, 0 1, 5 loyo 2.0 1.0

0.2 0.05

5

012 0> 2

lip O 1, O 0.3 bone

350 2 O

  4 y 1 1, 1 limpid lilq-, ide 0.01 1.0 0.3 QS 4, 1 Imride 1 A bone os QS

-300 150 20

4, 1 3.0 14.7

  limpid disorder disorder 0.3 QS 4.1 Trouble 1.0 0.3 QS 4) .1 Disorder

1.0 1.0

0.3 os QS

250,300

  1, 1 limpid disorder tn -Pl C) r 1 j CY% Note examples: We adjust the pH of each product studied between

2,7 and 3.

  1 Culminal MHPC 6000 from Henkel K Ga to Dusseldorf 2 Kelzan S

  3 BASF Aktiendicarboxylic acid mixture

  gesellschaft, D-6700, Ludwigshaven 4 Tensia's Tensophene D-36, Rhone Poulenc's Cemulsol NP 12, Dow Chemical's Dowfax 9 N 12, Symperonic NP 13's ICI 6 Tensia 7 Dobanol 91-8 Tensophene D 42 from Shell 8 Lutensol ON 80 D of BASF 9 Dobanol 25-11 of Shell 10 Ukanyl 87 of PC-UK 11 Ethylan CD 919 of Diamond Shamrock

  12 Rewominoxide amine oxide L 408 from Rewo.

  13 Mixture of 5-chloro-2-methyl-4-isothiazolin-3-

  Rohm and Haas 2-methyl-4-isothiazolin-3-one 14 Ugine-Kuhlmann blue dye From Hoechst 16 Emphos CS 141 from Witco Chemical 17 Triton X 305 from Rohm and Haas The examples show that viscosity depends on the concentration of the thickener When using the

  methylhydroxypropylcellulose, it can be seen that a concentration

  This gives a viscosity of about 350 cP (+ 50 cP). This is very satisfactory for maintaining sufficient contact between the acidic material and the scale.

  limestone to be eliminated Note that 0.3% gum xan-

  thane gives approximately the same results, except

  In this example, acetic acid apparently causes decomposition.

polysaccharide.

  It can be seen that the various levels of the organic acids of Examples 1-22, 26 and 28 are effective in removing scale from scale for cleaners

  for water closets, it is considered that

  These examples clearly show that a concentration of 5.0% of the mixture of adipic, glutaric and succinic acids provides an acceptable removal of calcareous scale (Examples 23 to 25). and 27 show that the

  sodium paraffin sulfonate and dodecylbenzenesulfonate

  sodium nate impede the removal of limescale scale).

  The use of xanthan gum produces solutions

  somewhat turbid, while the methylhy-

  This clear solution meets the requirements of consumers who desire a cleaning product with a good appearance and which does not seem to add a particulate or "dirty" material to the site to be cleaned. The use of bacteriostats, such as

  formaldehyde and isothiazolinones Kathon is illus-

  The nature of the thickeners is such that they must be protected against bacterial growth by

acidic condition.

  The invention has been described by illustrations

  and examples that do not limit it because it is obvious

  dent that is known to those skilled in the art to use substituents and the like without

depart from the scope of the invention.

Claims (11)

  A stable thickened acidic detergent composition comprising: a nonvolatile, water-soluble organic acid selected from fatty acids having 2 or 3 carbon atoms, dicarboxylic acids having 3 to 8 carbon atoms, hydroxycarboxylic acids containing 1 to 6 carbon atoms, 1 to 5 hydroxy groups and 1 to 3 carboxy groups, and mixtures thereof, a detergent selected from anionic, cationic, nonionic, zwitterionic and amphoteric surfactants, amine oxides, phosphoric acid and mixtures thereof, and a thickener based on a cellulose ether such that the composition has a pH between 2.2 and 3.5 and a viscosity of 150 to 800 centipoise.   Composition according to claim 1 in the   which organic acid is acetic acid, citric acid, succinic acid, glutaric acid, acid adipic acid or mixtures thereof.   Composition according to claim 2 in the   the organic acid is a mixture of 25 to 31% of   of succinic acid, 42 to 50% glutaric acid, and 25 to 33% of adipic acid.   Composition according to Claim 1, characterized   in that the detergent is a surfactant nonionic   Composition according to Claim 4, characterized in that the nonionic surfactant is selected from polyethylene oxide condensates with polyphenylene alkylphenols and polyethylene oxide condensates. with aliphatic alcohols.   A composition according to claim 5 in the   the nonionic surfactant is a nonylphene   condensed with 12 moles of ethylene oxide.   Composition according to Claim 5   wherein the surfactant is an alcohol   phaistic with 12 to 15 carbon atoms condensed with 11 moles of ethylene oxide.   8 Composition according to claim 1 in   which the cellulose ether is methylhydroxypropyl-   cellulose. The composition of claim 1 which contains from about 2% to about 7% by weight of an acid   organic non-volatile water soluble.   Composition according to claim 1 which   contains about 3% to about 7% by weight of a detergent.   The composition of claim 1 which contains from 0.5% to about 1.2% by weight of a thickener to base of a cellulose ether.   12 Composition according to claim 1 in   which p H is between 2.7 and 3.0.   A composition according to claim 1 which has a viscosity after aging of less than about 400 c. 14 A method for removing scale and rust stains from the surfaces of toilet bowls and the like which comprises applying a clear, thick acidic composition stable composition comprising (a) about 2 to 7% by weight of a mixture consisting essentially of 25 to 31% by weight of succinic acid, 42 to 50% by weight of glutaric acid and 25 to 33% by weight of acid adipic acid, (b) about 3 to about 7% by weight of a nonionic surfactant and (c) about 0.5 to 1.2% by weight of methylhydroxypropylcellulose, and having a p H of 2.7 to 3 , 0, to the surfaces of   cups of water closets, leave the composition   in contact with stained surfaces for at least   half an hour, and rinse the treated surfaces.