EP3623455B1 - Formulation détartrante pour toilettes - Google Patents

Formulation détartrante pour toilettes Download PDF

Info

Publication number
EP3623455B1
EP3623455B1 EP19196827.0A EP19196827A EP3623455B1 EP 3623455 B1 EP3623455 B1 EP 3623455B1 EP 19196827 A EP19196827 A EP 19196827A EP 3623455 B1 EP3623455 B1 EP 3623455B1
Authority
EP
European Patent Office
Prior art keywords
weight
descaling
formulation
formulation according
ranging
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.)
Active
Application number
EP19196827.0A
Other languages
German (de)
English (en)
Other versions
EP3623455A1 (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 RS20221184A priority Critical patent/RS63907B1/sr
Priority to SI201930414T priority patent/SI3623455T1/sl
Priority to HRP20221551TT priority patent/HRP20221551T1/hr
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

Links

Images

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.
  • compositions for cleaning hard surfaces comprising a generic pigment together with quaternary ammonium salt cationic surfactant, an aromatic organic salt anionic surfactant and a descaling agent.
  • 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 preferably ranges from 1,000:1 to 10:1, or 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 1.50000 Trade-name: Arlypon VPC, Basf Unsaturated ethoxylated C 16 -C 18 and C 18 alcohols, Trade-name: Arlypon VPC, Basf 0.50000
  • 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.
  • Test 1 Marble cube test, which involves immersing a cube of white Carrara marble, having a known weight and size, in the descaling liquid for certain times (5, 30 and 60 minutes). After careful rinsing and drying of the cube, its weight is measured to determine the percentage of CaCO 3 consumed by the product.
  • Test 2 Marble slab test, which involves immersing a slab of white Carrara marble, having a known weight and size, in the descaling liquid for a time equal to 10 seconds; the slab is then placed in a vertical position on a grid to allow the liquid to flow along the surface of the marble for a period of 10 minutes. After careful rinsing and drying of the slab, its weight is measured to determine the percentage of CaCO 3 consumed by the product. For both tests, the highest percentage of CaCO 3 removed corresponds to the best performance of the product.
  • 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.

Landscapes

  • 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Saccharide Compounds (AREA)

Claims (11)

  1. Formulation de détartrage pour WC, caractérisée en ce qu'elle comprend ou consiste en
    a) un agent viscosifiant constitué d'un tensioactif cationique et d'un tensioactif anionique choisis, respectivement, parmi les sels d'ammonium quaternaire et les sels d'acides organiques aromatiques forts, le rapport pondéral sels d'ammonium quaternaire/sels d'acides organiques aromatiques forts allant de préférence de 1000:1 à 10:1, ou de préférence de 5:1 à 4:1 ;
    b) un agent de pigmentation constitué de, ou comprenant une dispersion aqueuse colloïdale d'un polymère organique inerte constitué d'un copolymère styrène-acrylique, ayant un poids moléculaire moyen allant de 300 000 à 800 000 Daltons, de préférence égal à 500 000 Daltons, et une concentration de solides allant de 20 à 50% en poids, de préférence égale à 35% en poids ; et
    c) un agent de détartrage choisi parmi l'acide chlorhydrique, l'acide phosphorique, l'acide sulfurique ou l'acide sulfamique, de préférence l'acide chlorhydrique.
  2. Formulation selon la revendication 1, dans laquelle le sel d'ammonium quaternaire est choisi parmi les sels de formule générale (I)

            R1R2R3R4N+ Cl-     (I)

    où R1, R2, R3, R4, identiques ou différents les uns des autres, sont des groupes alkyle ou alkyl-aryle ayant un nombre d'atomes de carbone allant de 1 à 30, et est de préférence choisi parmi le chlorure de suif-triméthylammonium ou le chlorure d'hexadécyltriméthylammonium.
  3. Formulation selon une ou plusieurs des revendications précédentes, dans laquelle le sel d'un acide organique aromatique fort est choisi parmi les sulfonates de formule générale (II)

            R1-Ar-SO3Na     (II)

    dans laquelle R1 est un groupe alkyle ayant un nombre d'atomes de carbone allant de 1 à 30 et Ar est un groupe phényle, de préférence choisi parmi le sel de sodium de l'acide dodécylbenzènesulfonique, le sel de sodium de l'acide 4-méthylbenzènesulfonique et les mélanges correspondants.
  4. Formulation selon une ou plusieurs des revendications précédentes, dans laquelle l'agent viscosifiant a) est présent en une quantité allant de 0,1 à 10% en poids, le tensioactif cationique étant présent en une quantité allant de 0,09 à 9% en poids et le tensioactif anionique en une quantité allant de 0,01 à 1% en poids par rapport au poids total de la formulation de détartrage.
  5. Formulation selon une ou plusieurs des revendications précédentes, dans laquelle l'agent de pigmentation est une dispersion aqueuse colloïdale d'un polymère organique inerte, à savoir un copolymère styrène-acrylique, ayant un poids moléculaire moyen égal à 500 000 Daltons, et une concentration de solides égale à 35% en poids, en une quantité allant de 0,01 à 5% en poids par rapport au poids total de la formulation de détartrage.
  6. Formulation selon une ou plusieurs des revendications précédentes, dans laquelle l'agent de détartrage est choisi parmi l'acide chlorhydrique, de préférence l'acide chlorhydrique aqueux à 33% en poids.
  7. Formulation selon une ou plusieurs des revendications précédentes, dans laquelle l'agent de détartrage est de l'acide chlorhydrique aqueux à 33% en poids en une quantité allant de 0,1 à 60% en poids par rapport au poids total de la formulation de détartrage.
  8. Formulation selon une ou plusieurs des revendications précédentes, comprenant en outre un agent parfumant ou une fragrance en une quantité allant de 0,01 à 1% en poids par rapport au poids total de la formulation détartrante.
  9. Formulation selon une ou plusieurs des revendications précédentes, qui comprend ou consiste en
    a) un agent viscosifiant constitué de chlorure de suif-triméthylammonium ou de chlorure d'hexadécyltriméthyl-ammonium et d'un mélange de sel de sodium d'acide dodécylbenzènesulfonique et de sel de sodium d'acide 4-méthylbenzènesulfonique, dans un rapport pondéral sel d'ammonium quaternaire/mélange de sels de sodium allant de 5:1 à 4:1 ;
    b) un agent de pigmentation constitué d'une dispersion aqueuse colloïdale d'un copolymère styrène-acrylique, ayant un poids moléculaire moyen de 500 000 Daltons et une concentration de solides égale à 35% en poids ; et
    c) un agent de détartrage qui est de l'acide chlorhydrique aqueux à 33% en poids.
  10. Formulation selon une ou plusieurs des revendications précédentes, qui consiste en
    a) un agent viscosifiant constitué de 1,5% en poids de chlorure de suif triméthylammonium ou de chlorure d'hexadécyl-triméthylammonium et de 0,35% en poids d'un mélange de sel de sodium de l'acide dodécylbenzènesulfonique et de sel de sodium de l'acide 4-méthyl-benzènesulfonique ;
    b) un agent de pigmentation constitué de 0,6% en poids d'une dispersion aqueuse colloïdale d'un copolymère styrène-acrylique, ayant un poids moléculaire moyen de 500 000 Daltons et une concentration de solides égale à 35% en poids ;
    c) 41% en poids d'acide chlorhydrique aqueux à 33% en poids, comme agent de détartrage ;
    d) 0,1% en poids d'un parfum,
    le complément à 100 constitué d'eau.
  11. Utilisation de la formulation de détartrage selon une ou plusieurs des revendications de 1 à 10, pour l'application sur la surface des appareils sanitaires, de préférence pour l'application sur la surface des WC, comme agent de détartrage et détergent.
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
RS20221184A RS63907B1 (sr) 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
HRP20221551TT HRP20221551T1 (hr) 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 EP3623455A1 (fr) 2020-03-18
EP3623455B1 true 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)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2073233B (en) * 1980-04-03 1983-10-05 Arrow Chem Ltd Cleaning compositions
EP0832964A1 (fr) * 1996-09-19 1998-04-01 The Procter & Gamble Company Compositions de nettoyage liquides stables et épaisses
CN1284126A (zh) * 1997-11-26 2001-02-14 宝洁公司 在分散层状相中的含水洗涤组合物

Also Published As

Publication number Publication date
EP3623455A1 (fr) 2020-03-18
ES2934464T3 (es) 2023-02-22
SI3623455T1 (sl) 2023-04-28
HRP20221551T1 (hr) 2023-02-17
HUE061204T2 (hu) 2023-05-28
RS63907B1 (sr) 2023-02-28
PL3623455T3 (pl) 2023-04-11

Similar Documents

Publication Publication Date Title
EP0013585B1 (fr) Composition détergente liquide douce
US3950260A (en) Polyacrylates of selective viscosity as detergent builders
AU622396B2 (en) Built detergent compositions containing diethyleneglycoliminodiacetic acid
US3308067A (en) Polyelectrolyte builders and detergent compositions
US3213030A (en) Cleansing and laundering compositions
US3963649A (en) Liquid detergent composition
US3709825A (en) Cleaning composition
US20050124514A1 (en) Soap bar compositions comprising alpha sulfonated alkyl ester and polyhyridic alcohol and process for producing the same
BRPI0616043A2 (pt) composição detergente contendo alcoxilato de álcool ramificado e tensoativo compatibilizante, e método para uso
US3679592A (en) Cleansing and soil preventive composition
CA2182677C (fr) Compositions de nettoyage acides
US4486329A (en) Liquid all-purpose cleaner
US11299693B2 (en) High performance dishwasher compositions
US4283300A (en) Method and composition to inhibit staining of porcelain surfaces by manganese
CN101151357A (zh) 具有阳离子聚合物、皂和两性表面活性剂的织物软化组合物
US5096622A (en) Liquid detergent composition containing alkylbenzene sulfonate, alkyl ethonal ether sulfate, alkanolamide foam booster and magnesium and triethanolammonium ions
US4302350A (en) Method and composition to inhibit staining of porcelain surfaces by manganese
EP3623455B1 (fr) Formulation détartrante pour toilettes
CN101802160B (zh) 含吡咯烷酮的洗涤剂组合物
US3758419A (en) Cleansing and laundering compositions
BR112020000531A2 (pt) formulação de detergente.
US3356613A (en) Built detergent compositions containing a synergistic mixture of stp, nta, and sodium silicate
BRPI0720374A2 (pt) Composição detergente para lavagem de tecidos, processo de lavagem e uso da mesma.
US10975332B2 (en) Home care compositions
EP0018344A1 (fr) Procédé et composition pour inhiber l'encrassement des surfaces de porcelaine par le manganèse, et appareil doseur pour chasse d'eau utilisant ladite composition

Legal Events

Date Code Title Description
REG Reference to a national code

Ref country code: HR

Ref legal event code: TUEP

Ref document number: P20221551T

Country of ref document: HR

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200915

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/62 20060101ALN20220602BHEP

Ipc: C11D 1/22 20060101ALN20220602BHEP

Ipc: C11D 3/40 20060101ALI20220602BHEP

Ipc: C11D 3/37 20060101ALI20220602BHEP

Ipc: C11D 3/34 20060101ALI20220602BHEP

Ipc: C11D 3/04 20060101ALI20220602BHEP

Ipc: C11D 1/65 20060101AFI20220602BHEP

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/62 20060101ALN20220708BHEP

Ipc: C11D 1/22 20060101ALN20220708BHEP

Ipc: C11D 3/40 20060101ALI20220708BHEP

Ipc: C11D 3/37 20060101ALI20220708BHEP

Ipc: C11D 3/34 20060101ALI20220708BHEP

Ipc: C11D 3/04 20060101ALI20220708BHEP

Ipc: C11D 1/65 20060101AFI20220708BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/62 20060101ALN20220817BHEP

Ipc: C11D 1/22 20060101ALN20220817BHEP

Ipc: C11D 3/40 20060101ALI20220817BHEP

Ipc: C11D 3/37 20060101ALI20220817BHEP

Ipc: C11D 3/34 20060101ALI20220817BHEP

Ipc: C11D 3/04 20060101ALI20220817BHEP

Ipc: C11D 1/65 20060101AFI20220817BHEP

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/62 20060101ALN20220819BHEP

Ipc: C11D 1/22 20060101ALN20220819BHEP

Ipc: C11D 3/40 20060101ALI20220819BHEP

Ipc: C11D 3/37 20060101ALI20220819BHEP

Ipc: C11D 3/34 20060101ALI20220819BHEP

Ipc: C11D 3/04 20060101ALI20220819BHEP

Ipc: C11D 1/65 20060101AFI20220819BHEP

INTG Intention to grant announced

Effective date: 20220908

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1536317

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602019022802

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: HR

Ref legal event code: T1PR

Ref document number: P20221551

Country of ref document: HR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2934464

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20230222

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20230400126

Country of ref document: GR

Effective date: 20230307

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 41235

Country of ref document: SK

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230307

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1536317

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221207

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E061204

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230410

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230407

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602019022802

Country of ref document: DE

REG Reference to a national code

Ref country code: HR

Ref legal event code: ODRP

Ref document number: P20221551

Country of ref document: HR

Payment date: 20230725

Year of fee payment: 5

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20230911

Year of fee payment: 5

Ref country code: RO

Payment date: 20230801

Year of fee payment: 5

Ref country code: NL

Payment date: 20230926

Year of fee payment: 5

Ref country code: CZ

Payment date: 20230731

Year of fee payment: 5

Ref country code: BG

Payment date: 20230724

Year of fee payment: 5

26N No opposition filed

Effective date: 20230908

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SK

Payment date: 20230904

Year of fee payment: 5

Ref country code: SI

Payment date: 20230831

Year of fee payment: 5

Ref country code: RS

Payment date: 20230724

Year of fee payment: 5

Ref country code: PL

Payment date: 20230830

Year of fee payment: 5

Ref country code: HU

Payment date: 20230922

Year of fee payment: 5

Ref country code: HR

Payment date: 20230725

Year of fee payment: 5

Ref country code: GR

Payment date: 20230921

Year of fee payment: 5

Ref country code: FR

Payment date: 20230927

Year of fee payment: 5

Ref country code: BE

Payment date: 20230920

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: MT

Payment date: 20230823

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20231002

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230927

Year of fee payment: 5

Ref country code: CY

Payment date: 20230911

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AL

Payment date: 20230726

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: MK

Payment date: 20230905

Year of fee payment: 5

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602019022802

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230911

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230911

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230911

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221207