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Copolymer Comprising Units of Type a Deriving from Carboxylic Acid Monomers and Units of Type B Deriving from Sulfonic Acid Monomers

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Copolymer Comprising Units of Type a Deriving from Carboxylic Acid Monomers and Units of Type B Deriving from Sulfonic Acid Monomers (19) TZZ ¥_T (11) EP 2 896 637 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 22.07.2015 Bulletin 2015/30 C08F 293/00 (2006.01) C11D 3/37 (2006.01) (21) Application number: 14305084.7 (22) Date of filing: 21.01.2014 (84) Designated Contracting States: • Wilson, David James AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 60580 Coye la Foret (FR) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • Clavier, Julie PL PT RO RS SE SI SK SM TR 92600 Asnieres sur Seine (FR) Designated Extension States: • van Gramberen, Eric BA ME 95870 Bezons (FR) (71) Applicant: Rhodia Operations (74) Representative: Nony 93306 Aubervilliers Cedex (FR) 3, rue de Penthièvre 75008 Paris (FR) (72) Inventors: •Orizet,Céline 92340 Bourg la Reine (FR) (54) Copolymer comprising units of type A deriving from carboxylic acid monomers and units of type B deriving from sulfonic acid monomers (57) The present invention relates to a copolymer of type A and B with a molar ratio of units of type A to comprising units of type A deriving from carboxylic acid units of type B greater or equal to 1, wherein said units monomers and units of type B deriving from sulfonic acid of type A and units of type B are statistically distributed, monomers, said units of type A and B representing more said second block having a degree of polymerization DP 2 than 80 mol % of the total moles of units in the copolymer, such that DP2/DP1 ≥ 1. characterized in that it comprises at least: It also relates to new detergent compositions com- - one first block formed of at least 95 mol % of units of prisingsuch a copolymer,and to theuse of thiscopolymer type A and having a degree of polymerization DP 1 com- in a detergent composition, especially an ADW compo- prised between 5 and 150; and sition, to prevent, limit or eliminate the filming phenom- - one second block formed of at least 95 mol % of units ena. EP 2 896 637 A1 Printed by Jouve, 75001 PARIS (FR) EP 2 896 637 A1 Description [0001] The present invention relates to new copolymers and their use in detergent compositions, especially for Auto- matic Dishwashing (ADW) to reduce or eliminate the formation of films. 5 [0002] Commercial detergent formulations make it possible to efficiently clean industrial, domestic or communal sur- faces. A frequent disadvantage of the detergent formulations is however the formation on the cleaned surfaces of films. This is the case, for example, during the cleaning of dishes, especially the glassware, by hand or using a dishwasher. The films generally correspond to a uniform deposition all over the cleaned surface, especially the film may result from the formation of a mineral precipitate. This phenomenon is known under the term of "filming". Moreover, carbonate and 10 phosphate salts that are conventionally used in detergent compositions, or that may come from the soil, unfortunately contribute to the formation of films. [0003] Various dispersant polymers have been proposed to limit the filming phenomena. [0004] The present invention specifically aims to provide novel agents for detergent compositions that improve the anti-filming effect of the known detergent compositions. 15 [0005] One objective of the present invention is thus to replace all or part of the dispersant polymers currently used in detergent compositions while keeping or even improving the anti-filming effect. [0006] The present invention relates, according to a first one of its aspects, to a copolymer comprising units of type A deriving from carboxylic acid monomers and units of type B deriving from sulfonic acid monomers, said units of type A and B representing more than 80 mol % of the total moles of units in the copolymer, characterized in that it comprises 20 at least: - one first block formed of at least 95 mol % of units of type A and having a degree of polymerization DP 1 comprised between 5 and 150; and - one second block formed of at least 95 mol % of units of type A and B with a molar ratio of units of type A to units 25 of type B being greater or equal to 1, wherein said units of type A and units of type B are statistically distributed, said second block having a degree of polymerization DP 2 such that DP2/DP1 ≥ 1. [0007] In the continuation, the copolymer is denoted by "copolymer of the invention" or more simply "the copolymer". [0008] Within the context of the present invention, the expression "unit deriving from a monomer" denotes a unit which 30 can be obtained directly from said monomer by polymerization. For example, a unit deriving from acrylic acid monomer denotes a unit of formula -CH2-CH(COOH)- even if this unit has been obtained by polymerizing an acrylic acid ester, followed by hydrolysing. Thus, the terminology "unit deriving from a monomer" relates only to the final composition of the polymer and is independent of the polymerization process used to synthesize the polymer. [0009] The wording "first block" (also referred to as "block 1") and "second block" (also referred to as "block 2") are 35 used only for the purpose of designating each of the blocks; and in no way imply a linkage order in the copolymer of the invention, neither in the steps of its preparation process. [0010] Said units of type A of the first block may be identical to or different from said units of type A included in the second block. [0011] For a purpose of simplification only, the units of type A in said first block will be referred below as units A’, and 40 the units of type A in said second block will be referred below as units A". Thus, units A’ and units A" may be identical or different units of type A. [0012] Against all expectations, the inventors have discovered that it is thus possible to attain a detergent composition showing excellent performance in term of reduction of the filming phenomena, by using such a copolymer. [0013] In particular, as will be seen below, a copolymer of the invention exhibits an anti-filming effect better than that 45 provided by the statistical AA/AMPS copolymers, such as the one sold under the trademark Acusol ™ 587. [0014] In the rest of the text, the abbreviation "AA" refers to acrylic acid, "AMPS" to 2-acrylamido-2-methylpropanesul- fonate, and "SVS" to sodium vinyl sulfonate. [0015] According to another of its aspects, the present invention relates to a detergent composition comprising at least one copolymer defined previously. 50 [0016] The present invention proves more particularly advantageous with regard to ADW detergent compositions, in particular domestic ADW compositions. [0017] The present invention also relates, according to still another of its aspects, to the use of at least one copolymer as defined above, in a detergent composition, especially a ADW detergent composition, to prevent, limit or eliminate the filming phenomena. 55 [0018] The invention also relates to a process for preventing, limiting or eliminating the filming phenomena due to washing, especially in ADW, comprising the use of a detergent composition containing at least one copolymer as defined above. [0019] Other features, advantages and modes of application of the copolymer and detergent composition according 2 EP 2 896 637 A1 to the invention will emerge more clearly on reading the following description and examples. [0020] In the remainder of the text, the expressions "between ... and ...", "ranging from ... to ..." and "varying from ... to ..." are equivalent and are understood to mean that the limits are included, unless otherwise mentioned. 5 COPOLYMER OF THE INVENTION [0021] As specified previously, the copolymer used according to the invention is formed of at least 80 mol % of units deriving from carboxylic acid monomers (referred to as "units of type A" or to units A’ and A") and units deriving from sulfonic acid monomers (referred to as "units of type B"). 10 [0022] In particular, said units of type A and of type B may represent more than 85 mol % of the total moles of units in the copolymer, more particularly more than 90 mol %, in particular more than 95 mol %. [0023] The optional monomer units other than said units of type A and B may be of various types, for example phosph(on)ate, cationic, amine containing, polyalkylene oxide, zwitterionic, amido or alcohol, alkyl ester units. [0024] According to a particular embodiment, a copolymer of the invention may consist only of units of type A and 15 units of type B. Units of type A [0025] According to one particular embodiment of the invention, units of type A may derive from monomers selected 20 from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloro-acrylic acid, bromo acrylic acid, bromomethyl acrylic acid, alpha-cyano acrylic acid, beta methyl-acrylic acid, alpha-phenyl acrylic acid, beta-acryloxy propionic acid, beta-carboxyethyl acrylic acid (oligomerised acrylic acid sold under tradename Sipomer B-CEA), sorbic acid, alpha-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, beta-styryl acrylic acid, itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, vinyl benzoic acid, pentenic 25 acid, propyl acrylic acid, acetamido acrylic acid, maleimido propyl carboxylic acid and mixtures thereof. [0026] Preferentially, units of type A derive from monomers selected from the group consisting of acrylic acid, meth- acrylic acid, ethacrylic acid, alpha-chloro-acrylic acid, bromo acrylic acid, bromomethyl acrylic acid, alpha-cyano acrylic acid, beta methyl-acrylic acid, alpha-phenyl acrylic acid, beta-acryloxy propionic acid, Beta-Carboxyethyl acrylic acid (oligomerised acrylic acid sold under tradename Sipomer B-CEA), cinnamic acid, itaconic acid, maleic acid, glutaconic 30 acid, aconitic acid, fumaric acid, vinyl benzoic acid, propyl acrylic acid, maleimido propyl carboxylic acid and mixtures thereof.
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