EP3623455A1 - Formulation détartrante pour toilettes - Google Patents

Formulation détartrante pour toilettes Download PDF

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Publication number
EP3623455A1
EP3623455A1 EP19196827.0A EP19196827A EP3623455A1 EP 3623455 A1 EP3623455 A1 EP 3623455A1 EP 19196827 A EP19196827 A EP 19196827A EP 3623455 A1 EP3623455 A1 EP 3623455A1
Authority
EP
European Patent Office
Prior art keywords
weight
descaling
formulation
acid
formulation according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19196827.0A
Other languages
German (de)
English (en)
Other versions
EP3623455B1 (fr
Inventor
Vincenzo Russo
Cinzia Brignoli
Roberta MARELLI
Marco Oliva
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bolton Manitoba SpA
Original Assignee
Bolton Manitoba SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bolton Manitoba SpA filed Critical Bolton Manitoba SpA
Priority to HRP20221551TT priority Critical patent/HRP20221551T1/hr
Priority to SI201930414T priority patent/SI3623455T1/sl
Priority to RS20221184A priority patent/RS63907B1/sr
Publication of EP3623455A1 publication Critical patent/EP3623455A1/fr
Application granted granted Critical
Publication of EP3623455B1 publication Critical patent/EP3623455B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the present invention relates to a descaling formulation for application in WCs.
  • the descaling products for WCs that currently exist are products based on hydrochloric acid and are almost always formulated with rheology modifying systems to ensure a greater effectiveness on the vertical surfaces of the WC.
  • the flowing speed on the ceramic walls of the WC must in fact be reduced, thus increasing the contact time of the product with the limestone and thus obtaining the removal of a greater quantity of encrustation.
  • Another way of avoiding colour deposits on the walls of WCs is to use a white formulation that is then camouflaged with the ceramic of the WC.
  • a similar solution must, however, take into account the inherent difficulty in covering a base tending to yellow: with time, the white formulation in any case tends to turn from white to beige and even to brown.
  • the most common white pigment, titanium dioxide, is not capable of withstanding the pH conditions of descaling products of WCs for long, and it dissolves completely in a few days.
  • the fate of all the other mineral fillers (gypsum, carbonates, silicates) that can be used for the same purpose is similar.
  • the objective of the present invention is therefore to identify a descaling formulation for WC applications which overcomes the drawbacks of the formulations of the state of the art.
  • the quaternary ammonium salt can be selected from salts having general formula (I) R 1 R 2 R 3 R 4 N + Cl - (I) wherein R 1 , R 2 , R 3 , R 4 , the same as or different from each other, are alkyl or alkyl-aryl groups having a number of carbon atoms ranging from 1 to 30.
  • the quaternary ammonium salt is preferably selected from tallow-trimethylammonium chloride or hexadecyltrimethyl-ammonium chloride.
  • Tallow is a product of animal origin, consisting of a mixture of triglycerides of C 14 -C 18 , saturated and unsaturated, long-chain fatty acids.
  • the salt of a strong aromatic organic acid is preferably selected from sulfonates having general formula (II) R 1 -Ar-SO 3 Na (II) wherein R 1 is an alkyl group having a number of carbon atoms ranging from 1 to 30 and Ar is a phenyl group.
  • the salt of the strong aromatic organic acid is more preferably selected from dodecylbenzenesulfonic acid sodium salt, 4-methylbenzenesulfonic acid sodium salt and relative mixtures.
  • the weight ratio of quaternary ammonium salts/salts of strong aromatic organic acids ranges from 1,000:1 to 10:1, preferably from 5:1 to 4:1.
  • the viscosifying agent is present in the formulation according to the present invention in a quantity ranging from 0.1 to 10% by weight: more specifically, the cationic surfactant is present in a quantity ranging from 0.09 to 9% by weight and the anionic surfactant in a quantity ranging from 0.01 to 1% by weight with respect to the total weight of the descaling formulation.
  • the pigmenting agent is preferably a colloidal aqueous dispersion of an inert organic polymer, namely a styrene-acrylic copolymer, obtained by the polymerization of styrene and acrylic/methacrylic acid, having an average molecular weight ranging from 300,000 to 800,000 Daltons, preferably equal to 500,000 Daltons, and a concentration of solids ranging from 20 to 50% by weight, preferably equal to 35% by weight.
  • the molecular weight is a number average molecular weight.
  • the pigmenting agent is present in the formulation according to the present invention in a quantity ranging from 0.01 to 5% by weight with respect to the total weight of the descaling formulation.
  • the descaling agent is selected from hydrochloric acid, phosphoric acid, sulfuric acid or sulfamic acid; it is preferably hydrochloric acid, more preferably aqueous hydrochloric acid at 33% by weight.
  • the descaling agent is present in the formulation according to the present invention in a quantity ranging from 0.1 to 60% by weight, in the case of HCl at 33% by weight.
  • the formulation according to the present invention may optionally also comprise a perfuming agent or fragrance in a quantity ranging from 0.01 to 1% by weight with respect to the total weight of the descaling formulation.
  • the descaling formulation for WCs according to the present invention preferably comprises or consists of
  • the descaling formulation for WCs according to the present invention more preferably consists of:
  • the weight percentages always refer to the total weight of the descaling formulation for WCs according to the present invention.
  • a further object of the present invention therefore relates to the use of the descaling formulation according to the present invention for application on the surface of bathroom fixtures, preferably for application on the surface of WCs, as a descaling agent and detergent.
  • the particular viscosifying system of the formulation according to the present invention is based on the combination of a cationic surfactant such as a quaternary ammonium salt and an anionic surfactant, deriving from a strong aromatic organic acid.
  • Quaternary ammonium salts are compounds known for their high chemical stability in a very wide pH range: more specifically, the stability is particularly high in an acid environment, whereas with extremely alkaline pHs degradation by Hofmann elimination may occur. The chemical stability evidently also results in a lower tendency towards yellowing, a phenomenon mainly caused by the presence of free amines.
  • the micelles that are formed in the presence of the cationic surfactant can be disturbed by the addition of a suitable hydrotrope, with the formation of rod-like micellar species and a simultaneous increase in the viscosity. It should in fact be borne in mind that a descaling formulation for WCs must be characterized by specific viscosity characteristics in order to be able to function and remove encrustations efficiently.
  • Salts of carboxylic acids and organic phosphates were therefore excluded, whereas sulfates, theoretically excellent candidates, showed a tendency towards hydrolysis which made their use extremely non-recommendable.
  • Sulfonates and in particular the sodium salt of dodecylbenzenesulfonic acid, surprisingly proved to be particularly effective.
  • the viscosifying system according to the present invention reaches a lower viscosity with respect to the traditional formulations based on ethoxylated amines, it guarantees in any case a correct adhesion of the descaling formulation according to the present invention to the walls of the WC and consequently an effective descaling effect.
  • the descaling formulation according to the present invention can be characterized by a white pigmentation by the addition of a colloidal dispersion of inert organic polymers. This dispersion proved to be surprisingly stable even at a pH lower than 1.
  • styrene-acrylic copolymer which can be assimilated according to the INCI nomenclature with a polystyrene, i.e. having chemical properties similar to those of a polystyrene.
  • a fragrance can also be added to the aqueous mixture of hydrochloric acid, cationic surfactant, anionic surfactant and polystyrene dispersion, with a slight drop in the final viscosity.
  • the descaling formulation for WCs according to the present invention thus obtained has no performance differences, expressed as the quantity of calcium carbonate removed, with respect to traditional descaling products containing amines/ ethoxylated amine oxides and dyes.
  • Base composition of the reference product of the state of the art, containing HCl, amines and ethoxylated amine oxides Composition in raw materials % (w/w) Demineralized water 57.00000 Hydrochloric acid 33% 41.00000 Ethoxylated oleic amine Trade-name: Arlypon VPC, Basf 1.50000 Unsaturated ethoxylated C 16 -C 18 and C 18 alcohols, 0.50000 Trade-name: Arlypon VPC, Basf
  • Arlypon VPC is a mixture of ethoxylated oleic amine and ethoxylated unsaturated C 16 -C 18 and C 18 alcohols, in a 3: 1 weight ratio.
  • Base composition of the formulation according to the present invention containing HCl, quaternary ammonium salts and sulfonates Composition in raw materials %(w/w) Demineralized water 57.15000 Hydrochloric acid 33% 41.00000 tallow-trimethylammonium chloride 1.50000 Mixture of dodecylbenzenrsulfonic sodium salt and 4-methyl-benzenesulfonic acid sodium salt 0.35000 Trade-name: Marlon ARL, Sasol
  • Base composition of the formulation according to the present invention containing HCl, quaternary ammonium salts and sulfonates Composition in raw materials %(w/w) Demineralized water 57.15000 Hydrochloric acid 33% 41.00000 hexadecyltrimethylammonium chloride 1.50000 Mixture of dodecylbenzenrsulfonic sodium salt and 4-methyl-benzenesulfonic acid sodium salt 0.35000 Trade-name: Marlon ARL, Sasol
  • the acid titre is determined by classical volumetric titration with a standard solution of 0.1N NaOH and a phenolphthalein indicator.
  • the density is measured by means of a Mettler DA - 100 M microdensometer, injecting the sample directly into the U-tube of the instrument, after calibration with demineralized water.
  • the viscosity of the products is measured by a Ford cup with a 2 mm diameter hole, completely filling the instrument with the fluid under examination and measuring the time taken for its total emptying.
  • Example 4 The following performance tests were then carried out comparing the final formulation of Example 4 according to the present invention and the final formulation of Example 1 according to the state of the art.
  • the descaling power of a WC cleaner was evaluated with two performance tests suitable for measuring how much CaCO 3 (limestone) is consumed over time.
  • Figure 1 shows the two samples, the base formulation according to the state of the art of Example 1 (on the left) and the base formulation according to the present invention of Example 2 (on the right), stored at 40°C for three months: the different tendency towards yellowing of the base is evident.
  • the base formulation according to the state of the art of Example 1 has a substantially brown colour, whereas the base formulation according to the present invention of Example 2 is still completely transparent.
  • Figure 2 shows the descaling formulation according to the present invention of Example 4, stored at 5°C (left), 20°C (center) and 40°C (right) for three months: the colour stability of the product is evident, which is white and remains white even after storage for three months at 40°C.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Saccharide Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP19196827.0A 2018-09-12 2019-09-11 Formulation détartrante pour toilettes Active EP3623455B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
HRP20221551TT HRP20221551T1 (hr) 2018-09-12 2019-09-11 FORMULACIJA ZA UKLANJANJE KAMENCA ZA WC-e
SI201930414T SI3623455T1 (sl) 2018-09-12 2019-09-11 Formulacija za odstranjevanje vodnega kamna za WC
RS20221184A RS63907B1 (sr) 2018-09-12 2019-09-11 Formulacija za uklanjanje kamenca za wc-e

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT201800008545 2018-09-12

Publications (2)

Publication Number Publication Date
EP3623455A1 true EP3623455A1 (fr) 2020-03-18
EP3623455B1 EP3623455B1 (fr) 2022-12-07

Family

ID=64427078

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19196827.0A Active EP3623455B1 (fr) 2018-09-12 2019-09-11 Formulation détartrante pour toilettes

Country Status (7)

Country Link
EP (1) EP3623455B1 (fr)
ES (1) ES2934464T3 (fr)
HR (1) HRP20221551T1 (fr)
HU (1) HUE061204T2 (fr)
PL (1) PL3623455T3 (fr)
RS (1) RS63907B1 (fr)
SI (1) SI3623455T1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2073233A (en) * 1980-04-03 1981-10-14 Arrow Chem Ltd Cleaning compositions
EP0832964A1 (fr) * 1996-09-19 1998-04-01 The Procter & Gamble Company Compositions de nettoyage liquides stables et épaisses
WO1999027066A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Compositions aqueuses de nettoyage en phase dispersee lamellaire

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2073233A (en) * 1980-04-03 1981-10-14 Arrow Chem Ltd Cleaning compositions
EP0832964A1 (fr) * 1996-09-19 1998-04-01 The Procter & Gamble Company Compositions de nettoyage liquides stables et épaisses
WO1999027066A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Compositions aqueuses de nettoyage en phase dispersee lamellaire

Also Published As

Publication number Publication date
ES2934464T3 (es) 2023-02-22
HRP20221551T1 (hr) 2023-02-17
EP3623455B1 (fr) 2022-12-07
RS63907B1 (sr) 2023-02-28
SI3623455T1 (sl) 2023-04-28
HUE061204T2 (hu) 2023-05-28
PL3623455T3 (pl) 2023-04-11

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