Biodegradable graft polymers

Abstract

To provide novel graft polymers that, when used in compositions such as cleaning compositions, have beneficial properties with respect to biodegradability and / or their cleaning behavior. [Solution] The present invention relates to a novel graft polymer, the graft polymer comprising a block copolymer skeleton (A) as a graft base, the block copolymer skeleton (A) having polymer side chains (B) grafted thereto. The polymer side chains (B) are obtained by polymerization of at least one vinyl ester monomer (B1) and optionally an additional monomer, N-vinylpyrrolidone (B2). Most preferably, the block copolymer skeleton (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). The present invention further relates to a method for obtaining such a graft polymer, the method preferably carried out by free radical polymerization. Furthermore, the present invention relates to the use of such graft polymers in, for example, fabrics and home care products. Another subject of the present invention is the fabrics and home care products themselves that contain such graft polymers.

Description

Technical Field

[0001] The present invention relates to a novel graft polymer, which contains a block copolymer backbone (A) as a graft base, and the block copolymer backbone (A) has polymer side chains (B) grafted thereto. The polymer side chains (B) are obtained by polymerization of at least one vinyl ester monomer (B1) and optionally N-vinylpyrrolidone (B2) as any further monomer. Most preferably, the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). The present invention further relates to a method for obtaining such a graft polymer, which is preferably carried out by free radical polymerization. Furthermore, the present invention relates to the use of such a graft polymer, for example, in fabrics and home care products. Another subject of the present invention is fabrics and home care products themselves containing such a graft polymer.

Background Art

[0002] In various countries, initiatives to ban microplastics, especially those in cosmetics, have already been introduced. There is intense discussion not only about the ban on this insoluble microplastic but also about future requirements for soluble polymers used in consumer products. Therefore, it is highly desirable to identify new and better biodegradable components for such applications. This problem is particularly acute for polymers produced by radical polymerization based mainly on a carbon-only backbone (a backbone containing no heteroatoms such as oxygen). This is because a carbon-only backbone is particularly difficult for microorganisms to decompose. Even industrially important graft polymers produced radically with a polyethylene glycol backbone show only limited biodegradation in wastewater. However, the polymers described by the present invention are preferably produced by radical graft polymerization, resulting in enhanced biodegradability compared to the prior art.

[0003] WO 2007 / 138053 discloses amphiphilic graft polymers based on a water-soluble polyalkylene oxide (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), wherein the polymer has an average of less than 1 graft site per 50 alkylene oxide units and an average molar mass M of 3,000 to 100,000. However, WO 2007 / 138053 does not describe any skeletal materials based on block copolymers. Furthermore, WO 2007 / 138053 does not contain any disclosure regarding the biodegradability (also called "biodegradation") of each of the graft polymers disclosed therein.

[0004] Y. Zhang et al., J.Coll.Inter.Sci 2005, 285, 80, relate to the synthesis and characterization of specific grafted polymers based on a Pluronic™ type skeleton. The Pluronic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer is grafted with poly(vinylpyrrolidone) by free radical polymerization of vinylpyrrolidone in dioxane and simultaneous chain transfer to Pluronic. However, Y. Zhang does not disclose that the polymer side chains of each grafted polymer are based on vinyl ester monomers. Furthermore, Y. Zhang makes no disclosure regarding the biodegradability of the grafted polymers disclosed therein. Y. Zhang also does not include any disclosure regarding the use of such grafted polymers in fabrics and home care products.

[0005] WO 03 / 042262 relates to a graft polymer comprising (A) a polymer graft skeleton without monoethylene unsaturated units and (B) polymer side chains formed from copolymers of two different monoethylene unsaturated monomers (B1) and (B2), each containing a nitrogen-containing heterocycle, wherein the proportion of side chains (B) is 35 to 55% by weight of the total polymer. However, the graft polymer according to WO 03 / 042262 is not based on vinyl ester monomers in each polymer side chain grafted onto the skeleton. Furthermore, WO 03 / 042262 does not make any disclosure relating to the biodegradability of the graft polymer disclosed therein.

[0006] US-A 5,318,719 relates to a novel class of biodegradable water-soluble graft copolymers having enhancement, film formation prevention, dispersibility, and threshold crystallization inhibition properties, the graft copolymers comprising (a) an acid-functional monomer and optionally (b) another water-soluble monoethylenically unsaturated monomer copolymerizable with (a), grafted onto a biodegradable substrate comprising a polyalkylene oxide and / or polyalkoxy material. However, US-A 5,318,719 does not disclose the use of a block copolymer backbone in each graft polymer. Furthermore, each side chain of the graft polymer is required to contain a large amount of an acid-functional monomer, such as acrylic acid or methacrylic acid. Such types of acid monomers are not useful in the context of the present invention. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] WO 2007 / 138053 [Patent Document 2] WO 03 / 042262 [Patent Document 3] US-A 5,318,719 [Non-patent literature]

[0008] [Non-Patent Document 1] Y. Zhang et al., J.Coll.Inter.Sci 2005, 285, 80 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The object of the present invention is to provide novel graft polymers. Furthermore, these novel graft polymers must have beneficial properties with respect to biodegradability and / or their cleaning behavior when used in compositions such as cleaning compositions. [Means for solving the problem]

[0010] The purpose of this is, (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide, and the number of individual blocks (x) in the block copolymer skeleton (A) is an integer, where x is 3 to 10, and (B) Polymer side chains grafted onto the block copolymer skeleton, wherein the polymer side chains (B) are obtained by polymerization of at least one vinyl ester monomer (B1) and optionally an additional monomer such as N-vinylpyrrolidone (B2), and This is achieved by graft polymers, including those mentioned above.

[0011] The graft polymer according to the present invention can be used, for example, in cleaning compositions and / or fabrics and home care products. The graft polymer provides, for example, improved anti-re-adhesion and cleaning performance compared to corresponding polymers or graft polymers in the prior art with respect to the re-adhesion of dirt and the removal of stains. Furthermore, when used in such compositions or products, for example, in cleaning compositions and / or fabrics and home care products, the graft polymer according to the present invention provides improved biodegradability.

[0012] The enhanced biodegradable graft polymer according to the present invention can be advantageously used in cleaning and sanitizing compositions. In cleaning and sanitizing compositions, the graft polymer assists the removal of hydrophobic dirt from textiles or hard surfaces by surfactants, thereby improving the cleaning and sanitizing performance of the formulation. Furthermore, the graft polymer better disperses the removed dirt in the cleaning or sanitizing solution and prevents re-adhesion of the cleaned or sanitized material surface.

[0013] The term “block copolymer (backbone)” as used herein means that each polymer contains at least two (more than two) homopolymer subunits (blocks) linked by covalent bonds. A 2-block copolymer has two distinct blocks (homopolymer subunits), while a tri-block copolymer has three distinct blocks (homopolymer subunits), and so on. The number of individual blocks in such a block copolymer is not limited; therefore, an “n-block copolymer” contains n distinct blocks (homopolymer subunits). Within each individual block (homopolymer subunit), the size / length of such a block may vary. The minimum length / size of a block is based on (as minimum) two individual monomers. The understanding of the term “block copolymer” will be further defined hereafter, in particular, along with the definition of “tri-block copolymer” based on general formula (A1) or general formula (A2). [Modes for carrying out the invention]

[0014] The present invention will be described in further detail as follows.

[0015] The first subject of this invention is, (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide, and the number of individual blocks (x) in the block copolymer skeleton (A) is an integer, where x is 3 to 10, and (B) Polymer side chains grafted onto the block copolymer skeleton, wherein the polymer side chains (B) are obtained by polymerization of at least one vinyl ester monomer (B1) and optionally an additional monomer such as N-vinylpyrrolidone (B2), and This relates to graft polymers, including those mentioned above.

[0016] The ratio of the block copolymer backbone (A) to the polymer side chains (B) in the graft polymer according to the present invention is not limited to any specific value. Any ratio known to those skilled in the art can be used. However, it is understood that the graft polymer contains more than 0.2% by weight of polymer side chains (B) (relative to the total weight of the graft polymer). Preferably, the graft polymer contains more than 1% by weight of polymer side chains (B) (relative to the total weight of the graft polymer). More preferably, the graft polymer contains 20 to 95% by weight of the block copolymer backbone (A) and 5 to 80% by weight of polymer side chains (B) (relative to the total weight of the graft polymer).

[0017] Preferably, the graft polymer comprises a block copolymer backbone (A) in 40-85% by weight, more preferably 50-80% by weight, and even more preferably 55-75% by weight (relative to the total weight of the graft polymer), and polymer side chains (B) in 15-60% by weight, more preferably 20-50% by weight, even more preferably 20-50% by weight, and even more preferably 25-45% by weight.

[0018] The block copolymer skeleton (A) itself, as well as methods for producing such block copolymer skeletons, are known to those skilled in the art. Various types of such block copolymer skeletons are commercially available, for example, under the trademark series "Pluronic" (BASF SE, Ludwigshafen, Germany). Specific examples include Pluronic PE 6100, Pluronic PE 6800, or Pluronic PE 3100.

[0019] A suitable block copolymer skeleton (A) to be used in the present invention is described, for example, in EP-A0362688. In the present invention, it is preferable that the monomers used to prepare the individual blocks of the block copolymer skeleton (A) are added sequentially. However, during the transition of supply from one monomer to the other, a so-called "dirty structure" may be generated, in which a small number of monomers from each adjacent block may be contained in the individual block in question at the edges / boundaries of each block. However, it is preferable that the block copolymer skeleton (A) according to the present invention does not contain any so-called "dirty structure" or "dirty passage" at each boundary of the blocks.

[0020] With respect to the block copolymer skeleton (A) of the graft polymer according to the present invention, the block copolymer skeleton (A) is i) By polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, preferably by polymerization of ethylene oxide and 1,2-propylene oxide as monomers, and / or ii) One of the at least two monomers used is ethylene oxide, preferably the second monomer used is 1,2-propylene oxide, and / or iii) The number (x) of individual (alkylene oxide) blocks in the block copolymer backbone (A) is an integer, where x has a value of 3 to 5, more preferably x is 3 is preferred.

[0021] When x is even, typically the graft polymer contains end-capping groups. Suitable end-capping groups are described in detail hereinafter.

[0022] The graft polymer according to the present invention may have any molecular weight known to those skilled in the art. However, the graft polymer has a weight average molecular weight M of 1000 to 100000 g / mol, preferably 2000 to 45000 g / mol, more preferably 3000 to 30000 g / mol w and is preferably.

[0023] The graft polymer according to the present invention preferably has a low polydispersity. The graft polymer has a polydispersity M of less than 3, preferably less than 2.5, more preferably less than 2.3, most preferably in the range of 1.0 to 2.2 w / M n (M w = weight average molecular weight, M n = number average molecular weight; the polydispersity has no unit g / mol / g / mol ) and is preferably. M w and / or M n Each value of can be determined as described in the experimental section hereinafter.

[0024] The block copolymer skeleton (A) contained in the graft polymer according to the present invention may be capped at each end group of the skeleton or not (uncapped). Therefore, in the present invention, the block copolymer skeleton (A) may be capped at one or both end groups depending on the case, preferably the block copolymer skeleton (A) is not capped at both end groups, or if the block copolymer skeleton (A) is capped, the capping is C1~C 25 - This is done by alkyl groups.

[0025] In one embodiment of the present invention, the block copolymer backbone (A) is preferably a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).

[0026] In the context of the present invention, it is generally preferable that the graft polymer has a block copolymer skeleton (A) having a structure based on formula (A1) or formula (A2). Equation (A1) is defined as follows:

[0027] [ka] (In the formula, n is an integer in the range of 2 to 100, preferably 3 to 80. m is an integer in the range of 2 to 100, preferably 10 to 70, more preferably 14 to 54), or Equation (A2) is defined as follows:

[0028] [ka] (In the formula, o is an integer in the range of 2 to 100, preferably 5 to 50, more preferably 8 to 27. p is an integer in the range of 2 to 100, preferably 5 to 50, and more preferably 7 to 24.

[0029] The block copolymer (A) may contain varying levels of hydrophilic ethylene glycol, which affect the overall properties of the graft polymer. The total EO content (%EO), which represents the total amount of ethylene glycol units in the block copolymer, is defined as follows: %EO=m(EO) / (m(total skeleton)) In the formula, m(EO) is the total mass of ethylene glycol units, and m(total skeleton) is the total mass of the skeleton. The block copolymer may have low, moderate, or high %EO values, which affects not only biodegradability but also the performance of the laundry formulation. The range is defined as follows: - Low: 5-20% EO - Medium: 21-50% EO - High: 51-90% EO

[0030] With respect to the polymer side chain (B) contained in the graft polymer according to the present invention, it is preferable that the polymer side chain (B) is obtained by radical polymerization, and / or that at least one vinyl ester monomer (B1) is vinyl acetate or vinyl propionate, more preferably vinyl acetate.

[0031] As the vinyl ester monomer (B1), in addition to vinyl acetate or vinyl propionate, any further vinyl ester known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate, or vinyl benzoate may be used. When N-vinylpyrrolidone (B2) is used as any further monomer in the preparation of the polymer side chain (B) in the graft polymer according to the present invention, the ratio of the essential vinyl ester monomer (B1) to the further monomer (B2) may be any value known to those skilled in the art. However, the amount of vinyl ester monomer (B1) is usually not less than 1% by weight (relative to the sum of (B1) and (B2)). Therefore, the polymer side chain (B) can preferably be obtained by radical polymerization of 1 to 100% by weight of monomer (B1) (most preferably vinyl acetate) and 0 to 99% by weight of any further monomer, N-vinylpyrrolidone (B2).

[0032] However, in the context of the present invention, the polymer side chain (B) is (B1) 10 to 100% by weight, preferably 50 to 100% by weight, more preferably 75 to 100% by weight, of at least one vinyl ester monomer (B1) (relative to the sum of (B1) and (B2)) and (B2) 0 to 90% by weight, preferably 0 to 50% by weight, more preferably 0 to 25% by weight, of N-vinylpyrrolidone (B2) as a further monomer (relative to the sum of (B1) and (B2) It is preferable to obtain it by free radical polymerization.

[0033] The graft polymers of the present invention may contain a certain amount of ungrafted polymer ("ungrafted side chains") made from vinyl esters (for example, polyvinyl acetate if only vinyl acetate is used, and / or, if further monomers are used, homopolymers of vinyl esters and copolymers with other monomers). The amount of such ungrafted vinyl acetate homopolymers and copolymers may be high or low depending on the reaction conditions, but is preferably low. By lowering the amount in this way, the amount of grafted side chains is preferably increased. This lowering can be achieved by reaction conditions related to suitable reaction conditions, such as the amounts of vinyl esters and radical initiators, their relative amounts, and the amount of the backbone present. This is generally known to those skilled in the art.

[0034] The graft polymer of the present invention may be characterized by its degree of grafting (the number of graft sites of polymer side chains (B) on the block copolymer skeleton (A)). The degree of grafting may be high or low depending on the reaction conditions. Preferably, the degree of grafting is low.

[0035] The degree of grafting and the amount of ungrafted polymer can be adjusted to optimize performance in a particular area of ​​interest, such as a specific formulation (e.g., detergent), application area, or desired cleaning performance.

[0036] In the context of the present invention, it is even more preferable that the polymer side chain (B) is obtained by radical polymerization of at least one vinyl ester monomer (B1) (preferably vinyl acetate or vinyl propionate, more preferably vinyl acetate) in an amount of 100% by weight (relative to the total amount of monomers used).

[0037] In another embodiment of the present invention, the polymer side chain (B) of the graft polymer according to the present invention is completely or at least partially hydrolyzed after the graft polymer itself has been obtained. This means that the complete or at least partial hydrolysis of the polymer side chain (B) of the graft polymer is carried out after the polymerization process of the polymer side chain (B) is completed.

[0038] For this complete or at least partial hydrolysis of the polymer side chain (B) of the graft polymer according to the present invention, each side chain unit derived from at least one vinyl ester monomer (B1) is converted from its respective ester functional group to an alcohol functional group in the polymer side chain (B). It should be noted that the corresponding vinyl alcohol is not suitable for use as a monomer in the polymerization process of the polymer side chain (B) from a stability standpoint. To obtain an alcohol functional group (hydroxy substituent) in the polymer side chain (B) of the graft polymer according to the present invention, the alcohol functional group is typically introduced by hydrolysis of the ester functional group of the side chain.

[0039] From a theoretical standpoint, each ester functional group in the polymer side chain (B) can be replaced by an alcohol functional group (hydroxyl group). In such cases, the polymer side chain is completely hydrolyzed (saponified). It should be noted that when N-vinylpyrrolidone is used as a further monomer, hydrolysis typically does not occur at these units of the polymer side chain (B) derived from the N-pyrrolidone (B) used as the further monomer.

[0040] Hydrolysis can be carried out by any method known to those skilled in the art. For example, hydrolysis can be induced by the addition of a suitable base, such as sodium hydroxide or potassium hydroxide.

[0041] However, in this embodiment of the present invention, hydrolysis of the polymer side chain (B) is preferably carried out only partially, for example, to a maximum of 20% by weight, 40% by weight, or 60% by weight (relative to the total weight of the polymer side chain).

[0042] In this embodiment, the polymer side chain (B) is preferably hydrolyzed completely or partially after polymerization, preferably to a maximum of about 50% of the amount of at least one vinyl ester monomer (B1) used in polymerization.

[0043] However, in preferred embodiments of the present invention, the polymer side chain (B) is not hydrolyzed after polymerization.

[0044] In the context of the present invention, it is preferable that no other monomers are used in each polymerization process for obtaining the polymer side chain (B), other than at least one vinyl ester monomer (B1) as defined above and optionally an additional monomer, N-vinylpyrrolidone (B2). However, if any additional polymerizable monomers exist other than the monomers based on (B1) and optionally (B2), such monomers (other than B1 and B2) are present in amounts of less than 1% of the total amount of monomers used to obtain the polymer side chain (B). Preferably, the amount of the additional monomer is less than 0.5% by weight, more preferably less than 0.01% by weight, and most preferably, no additional monomers are present at all other than monomers (B1) and optionally (B2).

[0045] In the present invention, it is particularly preferable not to use any monomers containing acidic functional groups. In particular, the monomers used to obtain the polymer side chain (B) of the graft polymer according to the present invention do not include any acidic functional monomers selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinyl acetic acid, or acrylooxypropionic acid.

[0046] The polymer of the present invention has at least one, preferably two or more, of the following properties so that it can be successfully used in the various application fields targeted by the present invention: a) A certain level of biodegradation. Such biodegradation is tested as defined elsewhere herein. To exhibit commercially useful biodegradation, the percentage of biodegradation should be at least 25 percent, preferably at least 30%, more preferably at least 40%, and even more preferably at least 50%, for example, 35, 45, 55, 60, 65, 75, 80, 85 or more, up to a maximum of 100% (all percentages in weight %) are based on total solids content. b) The polymer should have water solubility to a certain extent so that it can be used in aqueous environments that are typically present in the application fields generally targeted by the present invention. Preferably, the polymer of the present invention should exhibit moderate to good, more preferably very good solubility in aqueous formulation environments that are typically used in various types of formulations, such as those related to dishwashing, automatic dishwashing, hard surface cleaning, fabric cleaning, fabric care, and cosmetic formulations. c) The viscosity of the polymer solution should be such that, in a reasonably high solid concentration of polymer (e.g., it may exist as a “pure” (then typically liquid) product dissolved in a solvent, typically an aqueous solution containing water and an organic solvent, water alone, or an organic solvent alone), the viscosity of such polymer or polymer solution should be within a range that allows typical technical process steps, such as pouring, pumping, dispensing, etc. Therefore, the viscosity should preferably be at least 10% by weight, more preferably at least 20%, even more preferably at least 40% by weight, and most preferably at least 50% by weight, for example, at least 60, 70, 80, or even 90% by weight of polymer concentration (based on the total solids of polymer in the solution, defined by the weight percentage of dry polymer in the total weight of the polymer solution), preferably in the range of less than about 4000 mPas at most, more preferably up to 3500 mPas at most, and even more preferably up to 3000 mPas at most, for example, up to 4500, 3750, 3250, 2750, or even less than 2600, for example, 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150, or 100 mPas. The viscosity can be measured at 25°C or at a higher temperature, for example, 50 or even 60°C. This enables suitable handling of polymer solutions on a commercial scale. Naturally, depending on the amount of solvent added, the viscosity decreases as the amount of solvent increases and vice versa, and is therefore clearly adjustable if desired. It is also clear that the measured viscosity depends on the temperature at the time of measurement; for example, the viscosity of a given polymer having a given solids content of 80% by weight will be higher at lower measurement temperatures and lower at higher measurement temperatures. In preferred embodiments, with no additional solvent added and the polymer in its as-prepared state, the solids content is between 70 and 99% by weight, more preferably between 75 and 85% by weight.In a more preferred embodiment, no additional solvent is added, and the polymer, in its as-prepared state, has a solids content between 70 and 99% by weight, more preferably between 75 and 95% by weight, and a viscosity, when measured at 60°C, is less than 3000 mPas, more preferably less than 3250 mPas, or even less than 2750, 2600, 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, or even less than 250 mPas.

[0047] To achieve these requirements, the following guidelines can be given regarding how to achieve such properties of the polymer of the present invention: Biodegradability is generally increased by at least one of the following conditions: • The molecular weight of the block copolymer skeleton (A) is low rather than high; • The weight percentage of polymer side chains (monomer B) grafted onto the backbone is lower than the weight percentage; • Choose skeletal structure A2 over A1; • The weight percentage of the ethylene oxide (EO) portion present in the skeleton (A) relative to the total alkylene oxide portion must be less than 80%, and even if further reduced, it must not fall below 10%.

[0048] A preferred graft polymer is obtained using at least one of the following conditions: I) The block copolymer backbone (A) has a number average molecular weight Mn of less than 3650 g / mol, preferably less than 3500, more preferably less than 3000 g / mol, even more preferably less than 2750 g / mol, and most preferably less than 2500 g / mol; • II) The weight percentage of polymer side chains of the graft polymer (monomer content (B) relative to the total weight of the graft polymer) is greater than 10, preferably at least 20, more preferably at least 40, even more preferably at least 35, 70 or less, more preferably 65 or less, even more preferably 60 or less, most preferably up to 55%, and up to 50% or less; • III) The graft polymer has a skeletal structure A2; IV) The weight percentage of the ethylene oxide (EO) portion of the graft polymer's skeleton (A) relative to the total alkylene oxide portion is less than 80%, and even lower, but not less than 10%.

[0049] A more preferable graft polymer can be obtained using one of the following combinations of conditions: (where "I", "II", etc., are defined in the previous paragraph) I+II, I+III I+II+III I+II+III+DIV

[0050] A more preferable graft polymer can be obtained using one of the following combinations of conditions: · I+II I+II+III

[0051] The most preferred graft polymer is obtained using the following combination of conditions: I+II+III

[0052] In one preferred embodiment of the present invention, the graft polymer has a triblock copolymer backbone (A) with a number-average molecular weight M n However, the polymer has a molecular weight of less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, and even more preferably less than 3000 g / mol, and the weight percentage of vinyl acetate (monomer B) grafted onto the backbone is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50.

[0053] In another preferred embodiment of the present invention, the graft polymer has a triblock copolymer backbone (A) with a number-average molecular weight M nHowever, the polymer has a molecular weight of less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, even more preferably less than 3000 g / mol, and most preferably less than 2500 g / mol, and the skeleton has structure A2, and the weight percentage of vinyl acetate (monomer B) grafted onto the skeleton is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50.

[0054] As a further criterion, it is naturally necessary to evaluate the individual performance of specific polymers and thereby rank them for each individual formulation in a particular application area. While a comprehensive overview is impossible due to the wide range of uses of the polymers of the present invention, this specification and examples provide guidance on how to prepare and select useful polymers with desired properties, and how to tailor those properties to desired needs. One such criterion in the field of home care, particularly fabric care, is naturally the cleaning performance, for example, the performance when a particular material exhibiting a certain stain is subjected to a given cleaning procedure.

[0055] The examples provide some guidance on the application of the method to the general field of fabric cleaning, i.e., fabric care.

[0056] Depending on individual needs for polymers exhibiting defined biodegradability, water solubility, and viscosity (i.e., handling properties), the general and specific teachings herein (not intended to be limited to the specific examples given) will serve as guidance on how to obtain such polymers.

[0057] Another subject of the present invention is a method for preparing the graft polymers of the present invention described above. In this method for obtaining at least one graft polymer according to the present invention, at least one monomer (B1) and optionally any monomer N-vinylpyrrolidone (B2) are polymerized in the presence of at least one block copolymer backbone (A).

[0058] It should be noted that the grafting process itself, in which a polymer backbone, such as a block copolymer backbone, is grafted with polymer side chains, is known to those skilled in the art. Any process known to those skilled in the art can be used in this invention.

[0059] In the method of the present invention, the polymer side chain (B) is preferably obtained by radical polymerization.

[0060] Radical polymerization itself is known to those skilled in the art. It is also known to those skilled in the art that the method of the present invention can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D). Each of these components is known to those skilled in the art.

[0061] When used in the context of this invention, the term "radical polymerization" includes not only free radical polymerization but also its variations, such as controlled radical polymerization. Preferred control mechanisms are RAFT, NMP, or ATRP, each of which, along with suitable control agents, are known to those skilled in the art.

[0062] The process according to the present invention is more preferably carried out by a method comprising polymerizing at least one monomer (B1) selected from vinyl acetate or vinyl propionate to obtain polymer side chains (B), and N-vinylpyrrolidone (B2) as an optional further monomer, in the presence of at least one block copolymer backbone (A), a free radical initiator (C), and optionally, at least one organic solvent (D) up to 50% by weight based on the sum of components (A), (B1), optionally (B2), and (C), at an average polymerization temperature having a decomposition half-life of 40 to 500 minutes, such that the fractions of unconverted graft monomers (B1) and optionally (B2) and initiator (C) in the reaction mixture are always quantitatively deficient relative to the block copolymer backbone (A).

[0063] The amount of the (free radical formation) initiator (C) is preferably 0.1 to 5% by weight, and particularly 0.3 to 3.5% by weight, based on the polymer side chain (B) in each case.

[0064] With respect to the process according to the present invention, it is preferable that the steady-state concentration of radicals present at the average polymerization temperature is substantially constant, and that the graft monomer (B1) or (B2) is always present in the reaction mixture only at low concentrations (e.g., 5% by weight or less). This makes it possible to control the reaction and prepare the graft polymer with a desired low polydispersity in a controlled manner.

[0065] The term "average polymerization temperature" here is intended to mean that, although the process is substantially isothermal, due to the exothermic nature of the reaction, there may be temperature variations that are preferably kept within a range of + / -10°C, more preferably within a range of + / -5°C.

[0066] According to the present invention, the (radical-forming) initiator (C) must have a decomposition half-life of 40 to 500 minutes, preferably 50 to 400 minutes, and more preferably 60 to 300 minutes, at the average polymerization temperature.

[0067] According to the present invention, the initiator (C) and graft monomer (B2) and / or (B2) are added in a manner that is advantageous, such that a low and substantially constant concentration of undegraded initiator and graft monomer (B1) and / or (B2) is present in the reaction mixture. The proportion of undegraded initiator in the whole reaction mixture is preferably 15% by weight or less, and particularly 10% by weight or less, based on the total amount of initiator added by weighing during monomer addition.

[0068] The average polymerization temperature is in the range of approximately 50 to 140°C, preferably 60 to 120°C, and more preferably 65 to 110°C.

[0069] A suitable initiator (C) having a decomposition half-life of 20 to 500 minutes in the temperature range of 50 to 140°C is - tert-C4~C 12 -Alkyl hydroperoxide and tert-(C9~C 12 -Aralkyl) Hydroperoxide O-C2~C 12 - Acylated derivatives, for example, tert-butylperoxyacetate, tert-butylmonoperoxymaleate, tert-butylperoxyisobutyrate, tert-butylperoxypivalate, tert-butylperoxyneoheptanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyneodecanoate, tert-amylperoxypivalate, tert-amylperoxy-2-ethylhexanoate, tert-amylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, tert-butylperoxybenzoate, tert-amylperoxybenzoate, and di-tert-butyldiperoxyphthalate. - tert-C8~C 14 - Di-O-C4~C alkylene bisperoxide 12- Acylated derivatives, for example, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene, - Ji (C2~C 12 -Alkanoyl) and dibenzoyl peroxides, for example, diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dicapryloyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide and di(2,4-dichlorobenzoyl) peroxide, - tert-C4~C5-alkylperoxy(C4~C 12 -Alkyl) carbonates, for example, tert-amylperoxy(2-ethylhexyl) carbonate, - Ji (C2~C 12 -Alkyl)peroxydicarbonates, for example, di(n-butyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate That is the case.

[0070] Examples of particularly suitable initiators (C) depending on the average polymerization temperature are: - At an average polymerization temperature of 50-60°C, tert-butylperoxyneoheptanoate, tert-butylperoxyneodecanoate, tert-amylperoxypivalate, tert-amylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, 1,3-di(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, - At an average polymerization temperature of 60-70°C, tert-butylperoxypivalate, tert-butylperoxyneoheptanoate, tert-butylperoxyneodecanoate, tert-amylperoxypivalate and di(2,4-dichlorobenzoyl)peroxide, - At an average polymerization temperature of 70-80°C, tert-butylperoxypivalate, tert-butylperoxyneoheptanoate, tert-amylperoxypivalate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl)peroxide and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, at an average polymerization temperature of -80 to 90°C, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl)peroxide, dibenzoyl peroxide and di(4-methylbenzoyl)peroxide, - At an average polymerization temperature of 90-100°C, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexanoate, tert-butylmonoperoxymaleate, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide and di(4-methylbenzoyl)peroxide, - At an average polymerization temperature of 100~110℃, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, and tert-amyl peroxy(2-ethylhexyl) carbonate, - At an average polymerization temperature of 110~120℃, tert-butyl monoperoxymaleate, tert-butylperoxy-3,5,5-trimethylhexanoate, and tert-amylperoxy(2-ethylhexyl) carbonate That is the case.

[0071] The preferred initiator (C) is O-C4-C5 alkyl hydroperoxide of tert-C4~C5 12 -These are acylated derivatives, with tert-butylperoxypivalate and tert-butylperoxy-2-ethylhexanoate being particularly preferred.

[0072] Particularly advantageous polymerization conditions can be easily established by precisely adjusting the initiator (C) and polymerization temperature. For example, preferred average polymerization temperatures are 60-80°C when using tert-butylperoxypivalate and 80-100°C when using tert-butylperoxy-2-ethylhexanoate.

[0073] The polymerization reaction of the present invention can preferably be carried out in the presence of a small amount of an organic solvent (D). It is also possible, of course, to use a mixture of different solvents (D). The preference is to use a water-soluble or water-miscible solvent.

[0074] When solvent (D) is used as a diluent, in each case, based on the sum of components (A), (B1), and optionally (B2), the amount used is generally 1 to 40% by weight, preferably 1 to 35% by weight, more preferably 1.5 to 30% by weight, and most preferably 2 to 25% by weight.

[0075] As an example of a suitable solvent (D), - Monohydric alcohol, preferably aliphatic C1-C1 16 - Alcohol, more aliphatic C2-C 12 -Alcohols, most preferably C2-C4 alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol. - Polyhydric alcohol, preferably C2-C 10-Diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene glycols, for example, ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol, - Alkylene glycol ether, preferably alkylene glycol mono(C1-C1) 12 -alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers, for example ethylene glycol monomethyl and -ethyl ethers and propylene glycol mono-methyl and -ethyl ethers. - Polyalkylene glycol, preferably poly(C2-C4-alkylene) glycol having 2 to 20 C2-C4-alkylene glycol units, more preferably polyethylene glycol having 2 to 20 ethylene glycol units and polypropylene glycol having 2 to 10 propylene glycol units, most preferably polyethylene glycol having 2 to 15 ethylene glycol units and polypropylene glycol having 2 to 4 propylene glycol units, for example diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol, - Polyalkylene glycol monoether, preferably poly(C2-C4-alkylene) glycol mono(C1-C) having 2 to 20 alkylene glycol units 25 -alkyl) ether, more preferably 2 to 20 alkylene glycol units, poly(C2-C4-alkylene) glycol mono(C1-C) 20 -alkyl) ether, most preferably poly(C2-C3-alkylene) glycol mono(C1-C) having 3-20 alkylene glycol units 16-alkyl) ethers, -carboxylic acid esters, preferably C1-C8 alkyl esters of C1-C6 carboxylic acids, more preferably C1-C4 alkyl esters of C1-C3 carboxylic acids, most preferably C2-C4 alkyl esters of C2-C3 carboxylic acids, for example, ethyl acetate and ethyl propionate. - Preferably an aliphatic ketone having 3 to 10 carbon atoms, for example, acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone. - Cyclic ethers, especially tetrahydrofuran and dioxane These are some examples.

[0076] The solvent (D) is also advantageously a solvent used to formulate the graft polymer of the present invention for use (e.g., in cleaning and decontamination compositions) and therefore may remain in the polymerization product.

[0077] Preferred examples of these solvents are polyethylene glycol having 2 to 15 ethylene glycol units, polypropylene glycol having 2 to 6 propylene glycol units, and especially alkoxylation products of C6-C8 alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0078] In this context, C8~C, which have a high degree of branching, are of particular priority. 16 -These are alkoxylated alcohol products, which enable the formulation of polymer mixtures that are free-flowing at 40-70°C and have a very low polymer content at relatively low viscosity. Branching may be present in the alkyl chain and / or polyalkoxylate moiety of the alcohol (copolymer of at least one propylene oxide, butylene oxide, or isobutylene oxide unit). Particularly preferred examples of these alkoxylated products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide, and C alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide. 13 / C 15Oxo alcohol or C 12 / C 14 Or C 16 / C 18 The preferred fatty alcohol is 2-propylheptanol, which is alkoxylated with 1–15 mol of ethylene oxide and 1–3 mol of propylene oxide.

[0079] In the process according to the present invention, a block copolymer backbone (A), graft monomers (B1), and optionally (B2), an initiator (C), and optionally a solvent (D) are typically heated in a reactor to a selected average polymerization temperature.

[0080] According to the present invention, polymerization is carried out in such a manner that an excess of polymer (block copolymer backbone (A) and formed graft polymer (B)) is always present in the reactor. The ratio of polymer to ungrafted monomer and initiator is generally 10:1 or higher, preferably 15:1 or higher, and more preferably 20:1 or higher.

[0081] The polymerization process according to the present invention can, in principle, be carried out in various types of reactors.

[0082] The reactor used is preferably a stirred tank, to which the block copolymer skeleton (A) is initially added whole or partially, along with graft monomers (B1) or (B2), initiator (C), and solvent (D), which are, if appropriate, a portion of the total amount, generally up to 15% by weight, and heated to polymerization temperature. The remaining amounts of (B), (C), and (D), if appropriate, are then added by weighing, preferably separately. The remaining amounts of (B), (C), and (D), if appropriate, are added by weighing over a period of preferably 2 hours or more, more preferably 4 hours or more, and most preferably 5 hours or more.

[0083] In a particularly preferred, substantially solvent-free modification of the process, the entire block copolymer backbone (A) is initially added as a molten material, and the graft monomer (B1) and, if appropriate, (B2), and preferably an initiator (C) present in the form of a 10-50 wt% solution of one of the solvents (D), are also weighed in, while controlling the temperature so that the selected polymerization temperature is maintained on average within a range of + / -10°C, particularly + / -5°C, during polymerization.

[0084] In a particularly preferred variant of the low-solvent process, the procedure is as described above, except that solvent (D) is added by metering during polymerization to limit the viscosity of the reaction mixture. It is also possible to start metering and adding the solvent only at a later time as polymerization progresses, or to add the solvent in installments.

[0085] Polymerization can be carried out under standard pressure, reduced pressure, or increased pressure. If the boiling point of the monomer (B1) or (B2) used, or any diluent (D), exceeds the boiling point at the selected pressure, polymerization is carried out under reflux cooling.

[0086] Another subject of the present invention is the use of at least one of the above-described graft polymers in laundry detergents, cleaning compositions, and / or fabric and home care products.

[0087] Further subject matter of the present invention is laundry detergents, cleaning compositions, and / or fabrics and home care products containing at least one of the graft polymers described above.

[0088] Laundry detergents, cleaning compositions, and / or fabrics and home care products themselves are known to those skilled in the art. Any composition, etc., known to those skilled in the art, related to their respective uses, can be used in the context of the present invention.

[0089] The present invention relates to a laundry detergent, a cleaning composition, and / or fabric and home care product, wherein at least one graft polymer is preferably present in an amount ranging from about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5%, relative to the total weight of such composition or product.

[0090] In addition, laundry detergents and cleaning compositions generally include surfactants, and, where appropriate, other polymers, builders, and further common components as cleaning substances, such as cobuilders, complexing agents, bleaches, standardizers, graying inhibitors, color transfer inhibitors, enzymes, and fragrances.

[0091] The graft polymer of the present invention is C 10 ~C 15 It may be used in laundry detergents or cleaning compositions comprising a surfactant system containing alkylbenzene sulfonate (LAS) and one or more co-surfactants selected from nonionic, cationic, anionic, or mixtures thereof. The selection of co-surfactants may depend on the desired benefit. In one embodiment, the co-surfactant is a nonionic surfactant, preferably C 12 ~C 18 Selected as an alkyl ethoxylate. In another embodiment, the co-surfactant is an anionic surfactant, preferably C 10 ~C 18 Alkylalkoxysulfate (AE x S) (where x is 1 to 30) is selected. In another embodiment, the co-surfactant is selected as a cationic surfactant, preferably dimethylhydroxyethyl laurylammonium chloride. The surfactant system is C 10 ~C 15 If alkylbenzene sulfonate (LAS) is included, the LAS is preferably used in a level ranging from about 9% to about 25% by weight, or about 13% to about 25% by weight, or about 15% to about 23% by weight of the composition.

[0092] The surfactant system may contain one or more cosurfactants selected from nonionic cosurfactants, cationic cosurfactants, anionic cosurfactants, and any mixtures thereof, in an amount of 0% to about 15% by weight, or about 0.1% to about 7% by weight, or about 1% to about 4% by weight of the composition.

[0093] As a non-limiting example of a nonionic copolymer, C 12 ~C 18 Alkyl ethoxylates, for example, Shell's NEODOL® nonionic surfactant; C6~C 12 Alkylphenol alkoxylates (alkoxylate units are mixtures of ethylene oxy units and propylene oxy units); C60 of ethylene oxide / propylene oxide block alkyl polyamine ethoxylates such as BASF's PLURONIC®. 12 ~C 18 Alcohol and C6~C 12 Alkylphenol condensates; C as discussed in US 6,150,322 14 ~C 22 Medium-chain branched alcohols, such as those discussed in BA;US 6,153,577, US 6,020,303, and US 6,093,856, are C 14 ~C 22 Medium-chain branched alkyl alkoxylates, BAE x (where x is between 1 and 30); examples include alkyl polysaccharides, as discussed in US 4,565,647 (Llenado, published January 26, 1986); specifically, alkyl polyglycosides, as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides, as discussed in US 5,332,528; and ether-capped poly(oxyalkylated) alcohol surfactants, as discussed in US 6,482,994 and WO 01 / 42408.

[0094] Non-limiting examples of semipolar nonionic copolymers include water-soluble amine oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of about 10 to about 18 carbon atoms and moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing about 1 to about 3 carbon atoms. See WO 01 / 32816, US 4,681,704, and US 4,133,779.

[0095] A non-limiting example of a cationic cosurfactant is a quaternary ammonium surfactant, which can have up to 26 carbon atoms. These include alkoxylate quaternary ammonium (AQA) surfactants, as discussed in US 6,136,769; dimethylhydroxyethyl quaternary ammonium, as discussed in US 6,004,922; dimethylhydroxyethyl laurylammonium chloride; polyamine cationic surfactants, as discussed in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005, and WO 98 / 35006; cationic ester surfactants, as discussed in U.S. Patents 4,228,042, 4,239,660, 4,260,529, and US 6,022,844; and amino surfactants, specifically amidopropyl dimethylamine (APA), as discussed in US 6,221,825 and WO 00 / 47708.

[0096] As a non-limiting example of anionic cosurfactants useful in this specification, C 10 ~C 20 Primary, branched, and random alkyl sulfates (AS); C 10 ~C 18Secondary (2,3) alkyl sulfate; C 10 ~C 18 Alkylalkoxysulfate (AE x S) (where x is between 1 and 30); C containing 1 to 5 ethoxy units 10 ~C 18 Examples include alkylalkoxycarboxylates; medium-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; medium-chain branched alkylalkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonates (MLAS); methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS) as discussed in WO 99 / 05243, WO 99 / 05242 and WO 99 / 05244.

[0097] The present invention relates to the graft polymer of the present invention and C8~C 18 The present invention may also relate to compositions comprising surfactant systems containing linear alkyl sulfonate surfactants and co-surfactants. The compositions may be in any form, namely, liquid; solid, e.g., powder, granules, pellets, paste, tablet, pouch, bar, gel; emulsion; type delivered in a two-compartment container; spray or foam detergent; pre-moistened wipes (i.e., cleaning compositions combined with nonwoven materials, e.g., as discussed in US 6,121,165 (Mackey et al.)); dry wipes activated with water by the consumer (i.e., cleaning compositions combined with nonwoven materials, e.g., as discussed in US 5,980,931 (Fowler et al.)); and other homogeneous or multiphase consumer cleaning products.

[0098] In one embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition. In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition, preferably impregnated into a nonwoven fabric substrate. As used herein, “impregnated” means that the hard surface cleaning composition is placed in contact with the nonwoven fabric substrate so that the hard surface cleaning composition permeates at least a portion of the nonwoven fabric substrate, preferably so that the nonwoven fabric substrate is saturated with the hard surface cleaning composition. The cleaning composition may also be used in car care compositions to clean various surfaces, such as hardwood, tile, ceramic, plastic, leather, metal, and glass. The cleaning composition may also be designed for use in personal care and pet care compositions, such as shampoo compositions, body washes, liquid or solid soaps, and other cleaning compositions in which surfactants come into contact with free hardness, as well as all compositions requiring a hardness-resistant surfactant system, such as oil drilling compositions.

[0099] In another embodiment, the cleaning composition is a dishwashing cleaning composition, such as a liquid dishwashing handwashing composition, a solid automatic dishwasher composition, a liquid automatic dishwasher composition, and an automatic dishwasher composition in tab / unit dose form.

[0100] Very typically, the cleaning compositions described herein, such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic and soap-based laundry bars, fabric softeners and liquid and solid fabric treatments, and all kinds of treatment articles, require several auxiliary agents, however, certain simply formulated products, such as bleaching additives, may require only, for example, oxygen bleaches and surfactants as described herein. A comprehensive list of suitable laundry or cleaning auxiliary materials can be found in WO 99 / 05242.

[0101] Common cleaning aids include builders, enzymes, polymers not discussed above, bleaches, bleach activators, and catalytic materials, excluding any materials already defined above. Other cleaning aids as used herein include a variety of active ingredients or special materials other than those mentioned above, such as foaming agents and defoaming agents, for example, dispersant polymers (e.g., those from BASF Corp. or Rohm & Haas), color speckles, silver care products, tarnish and / or corrosion inhibitors, dyes, fillers, alkaline sources, hydrotropes, antioxidants, enzyme stabilizers, pro-fragrances, fragrances, solubilizers, carriers, processing aids, pigments, and, in the case of liquid formulations, solvents, chelating agents, color transfer inhibitors, dispersants, whitening agents, defoaming agents, dyes, structural elastomates, fabric softeners, abrasion inhibitors, hydrotropes, processing aids, and other fabric care, surface and skin care agents. Suitable examples of other such cleaning aids and levels of use can be found in U.S. Patent Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1.

[0102] How to use The present invention includes a method for cleaning a target surface. As used herein, “target surface” can refer to, for example, surfaces such as cloth, tableware, glass, and other cookware surfaces, hard surfaces, hair, or skin. As used herein, “hard surface” can refer to hard surfaces typically found in homes, such as hardwood, tile, ceramic, plastic, leather, metal, and glass. Such a method includes the steps of bringing a composition containing a modified polyol compound (in an undiluted form or diluted with a cleaning solution) into contact with at least a portion of the target surface, and optionally rinsing the target surface. Preferably, the target surface is subjected to the cleaning step before any of the rinsing steps described above. For the purposes of the present invention, cleaning methods include, but are not limited to, scrubbing, wiping, and mechanical stirring.

[0103] As those skilled in the art will understand, the cleaning compositions of the present invention are ideally suited for use in home care (hard surface cleaning compositions) and / or laundry applications.

[0104] The pH of the composition solution is selected to be most favorable to the target surface to be cleaned, and it ranges from about 5 to about 11. For personal care such as skin and hair cleansing, the pH of such a composition is preferably about 5 to about 8, and for laundry cleansing compositions, it is about 8 to about 10. The composition is preferably used at a concentration of about 200 ppm to about 10,000 ppm in the solution. The water temperature is preferably in the range of about 5°C to about 100°C.

[0105] When used in laundry cleaning compositions, the composition is preferably used at a concentration of about 200 ppm to about 10,000 ppm in the solution (or cleaning solution). The water temperature is preferably in the range of about 5°C to about 60°C. The ratio of water to fabric is preferably about 1:1 to about 20:1.

[0106] The method may include the step of bringing into contact a nonwoven fabric substrate impregnated with the composition of the embodiment of the present invention. As used herein, “nonwoven fabric substrate” can include any conventional nonwoven fabric sheet or web having suitable basis weight, paper thickness, absorbency and strength properties. Examples of suitable commercially available nonwoven fabric substrates include those sold by DuPont under the trademark name SONTARA® and those sold by James River Corp. under the trademark name POLYWEB®.

[0107] As those skilled in the art will understand, the cleaning composition of the present invention is ideally suited for use in liquid dishwashing cleaning compositions. A method for using the liquid dishwashing composition of the present invention comprises the step of bringing soiled dishes into contact with an effective amount, typically about 0.5 ml to about 20 ml (per 25 dishes to be treated), of the liquid dishwashing cleaning composition of the present invention diluted in water.

[0108] Another subject of the present invention is the use of at least one graft polymer in laundry detergents, cleaning compositions, and / or fabric and home care products, wherein the graft polymer is (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide; and (B) Polymer side chains grafted onto the block copolymer skeleton, wherein the polymer side chains (B) are obtained by polymerization of at least one vinyl ester monomer (B1) selected from vinyl acetate or vinyl propionate, and optionally an additional monomer such as N-vinylpyrrolidone (B2); This includes use.

[0109] In this particular subject of the present invention, the number of individual blocks (x) in the block copolymer skeleton (A) is preferably an integer, where x has a value of 2 to 10, preferably x has a value of 2 to 5, more preferably x is 2 or 3, and most preferably x is 3.

[0110] Furthermore, this particular subject also includes all the preferred, more preferred, etc. definitions / characteristics as described above in relation to the definition of the graft polymer itself, provided that at least one vinyl ester monomer (B1) is selected from vinyl acetate or vinyl propionate.

[0111] Further subject matter of the present invention is therefore laundry detergents, cleaning compositions, and / or fabrics and home care products, (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide, and (B) A polymer side chain grafted onto a block copolymer skeleton, wherein the polymer side chain (B) is obtained by polymerization of at least one vinyl ester monomer (B1) selected from vinyl acetate or vinyl propionate, and optionally an additional monomer, N-vinylpyrrolidone (B2), and A laundry detergent, cleaning composition, and / or fabric and home care product containing at least one graft polymer including the above.

[0112] Preferably, in each laundry detergent, cleaning composition, and / or fabric and home care product, at least one graft polymer is present in an amount ranging from about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5%, relative to the total weight of such composition or product.

[0113] Further embodiments of the present invention include: (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide, and (B) A polymer side chain grafted onto a block copolymer skeleton, wherein the polymer side chain (B) is obtained by polymerization of at least one vinyl ester monomer (B1) and optionally an additional monomer, N-vinylpyrrolidone (B2), and This relates to graft polymers, including those mentioned above.

[0114] In this particular subject matter of the present invention, the number of individual blocks (x) in the block copolymer skeleton (A) is preferably an integer, where x has a value of 2 to 10, preferably x has a value of 2 to 5, more preferably x is 2 or 3, and most preferably x is 3. Furthermore, this particular embodiment also includes all preferred, more preferred, etc. definitions / features as described above in relation to other embodiments of the present invention.

[0115] The following specific embodiments are incorporated into the Invention as particularly preferred embodiments. Herein, various further options are disclosed herein as “any,” “preferred,” “more preferred,” “even more preferred,” or “most preferred” options and choices / preferentialities that can be combined in any of the following embodiments, and such combinations are included either with each individual option or preference alone, or with at least one of any other options and / or preferences. Thus, all these possible combinations are specifically incorporated into the Invention.

[0116] Embodiment 1 (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide, and the number of individual blocks (x) in the block copolymer skeleton (A) is an integer, where x has a value of 3 to 5, and more preferably x is 3, and the block copolymer skeleton, (B) A polymer side chain grafted onto a block copolymer skeleton, wherein the polymer side chain (B) is obtained by polymerization of at least one vinyl ester monomer (B1) and optionally an additional monomer, N-vinylpyrrolidone (B2), and A graft polymer containing [a specific compound / component].

[0117] Embodiment 2 The graft polymer according to Embodiment 1, comprising 20 to 95% by weight of a block copolymer skeleton (A) and 5 to 80% by weight of polymer side chains (B) (relative to the total weight of the graft polymer), preferably comprising 40 to 85% by weight, more preferably 50 to 75% by weight of a block copolymer skeleton (A) and preferably 15 to 60% by weight, more preferably 25 to 50% by weight of polymer side chains (B) (relative to the total weight of the graft polymer).

[0118] Embodiment 3 The block copolymer skeleton (A) i) obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, or 1,2-butylene oxide, preferably by polymerization of ethylene oxide and 1,2-propylene oxide as monomers, and / or ii) At least one of the two monomers used is ethylene oxide, preferably the second monomer used is 1,2-propylene oxide, and / or iii) The number of individual blocks (x) in the block copolymer skeleton (A) is an integer, where x has a value between 3 and 5, and more preferably x is 3. A graft polymer according to Embodiment 1 or 2.

[0119] Embodiment 4 i) The graft polymer has a weight-average molecular weight M of 1,000 to 100,000 g / mol, preferably 2,000 to 45,000 g / mol, and more preferably 3,000 to 30,000 g / mol. w Having, and / or ii) The graft polymer has a polydispersity M of less than 3, preferably less than 2.5, more preferably less than 2.3, and most preferably in the range of 1.0 to 2.2. w / M n (M w = weight average molecular weight, M n =number average molecular weight[ g / mol / g / mol ]) has and / or iii) The block copolymer skeleton (A) may be capped at one or both of its end groups, preferably the block copolymer skeleton (A) is not capped at both end groups, or if the block copolymer skeleton (A) is capped, the capping is C1-C 25 - Made by alkyl groups and / or iv) The block copolymer skeleton (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). A graft polymer according to any one of Embodiments 1 to 3.

[0120] Embodiment 5 The block copolymer skeleton (A) has a structure based on formula (A1) or formula (A2), where formula (A1) is defined as follows:

[0121] [ka] (In the formula, n is an integer in the range of 2 to 100, preferably 3 to 80. m is an integer in the range of 2 to 100, preferably 10 to 70, more preferably 14 to 54), or Equation (A2) is defined as follows:

[0122] [ka] (In the formula, o is an integer in the range of 2 to 100, preferably 5 to 50, more preferably 8 to 27. p is an integer in the range of 2 to 100, preferably 5 to 50, more preferably 7 to 24. A graft polymer according to any one of Embodiments 1 to 4.

[0123] Embodiment 6 The graft polymer according to any one of Embodiments 1 to 5, wherein the polymer side chain (B) is obtained by radical polymerization, and / or at least one vinyl ester monomer (B1) is vinyl acetate or vinyl propionate, more preferably vinyl acetate.

[0124] Embodiment 7 i) The polymer side chain (B) is obtained by polymerization in the presence of N-vinylpyrrolidone (B2) as a further monomer, and / or ii) The polymer side chain (B) is completely or partially hydrolyzed after polymerization, preferably to a maximum of 50% of the amount of at least one vinyl ester monomer (B1) used in polymerization. A graft polymer according to any one of Embodiments 1 to 6.

[0125] Embodiment 8 The polymer side chain (B) (B1) 25 to 100% by weight, preferably 50 to 100% by weight, more preferably 75 to 100% by weight, of at least one vinyl ester monomer (B1) (relative to the sum of (B1) and (B2)), (B2) 0 to 75% by weight, preferably 0 to 50% by weight, more preferably 0 to 25% by weight, of N-vinylpyrrolidone (B2) as a further monomer (relative to the sum of (B1) and (B2) A graft polymer according to any one of Embodiments 1 to 7, obtained by radical polymerization.

[0126] Embodiment 9 The graft polymer according to any one of Embodiments 1 to 8, wherein the polymer side chain (B) is obtained by radical polymerization of at least one vinyl ester monomer (B1) in an amount of 100% by weight (relative to the total amount of monomers used), and the vinyl ester monomer (B1) is preferably vinyl acetate or vinyl propionate, and more preferably vinyl acetate.

[0127] Embodiment 10 Number average molecular weight M of the triblock copolymer skeleton (A) n The graft polymer according to any one of Embodiments 1 to 9, wherein the concentration is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, and even more preferably less than 3000 g / mol.

[0128] Embodiment 11 A graft polymer according to any one of Embodiments 1 to 10, wherein the weight percentage of vinyl acetate (monomer B) grafted onto the skeleton is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50.

[0129] Embodiment 12 A graft polymer according to any one of Embodiments 1 to 11, wherein the skeleton has structure A2.

[0130] Embodiment 13 A graft polymer according to any one of Embodiments 1 to 12, wherein the weight percentage of ethylene oxide (EO) in the backbone is at least 10% and 80% or less, preferably at least 20%, and preferably 70% or less.

[0131] Embodiment 14 Number average molecular weight M of the triblock copolymer skeleton (A) n The graft polymer according to any one of Embodiments 1 to 9, wherein the molecular weight is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, and even more preferably less than 3000 g / mol, and the weight percentage of vinyl acetate (monomer B) grafted onto the backbone is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50.

[0132] Embodiment 15 Number average molecular weight M of the triblock copolymer skeleton (A) n The graft polymer according to any one of Embodiments 1 to 9, wherein the amount is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, even more preferably less than 3000 g / mol, and most preferably less than 2500 g / mol, and the skeleton has structure A2.

[0133] Embodiment 16 Number average molecular weight M of the triblock copolymer skeleton (A) n However, it is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, even more preferably less than 3000 g / mol, and most preferably less than 2500 g / mol. The skeleton has structure A2, The weight percentage of vinyl acetate (monomer B) grafted onto the skeleton is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50. A graft polymer according to any one of Embodiments 1 to 9.

[0134] Embodiment 17 Number average molecular weight M of the triblock copolymer skeleton (A) n However, it is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, even more preferably less than 3000 g / mol, and most preferably less than 2500 g / mol. The skeleton has structure A2, The weight percentage of vinyl acetate (monomer B) grafted onto the skeleton is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and most preferably less than 70, more preferably less than 60, and most preferably less than 50. The weight percentage of ethylene oxide (EO) in the skeleton is at least 10% and 80% or less, preferably at least 20% and preferably 70% or less. A graft polymer according to any one of Embodiments 1 to 9.

[0135] Embodiment 18 A method for obtaining at least one graft polymer according to any one of Embodiments 1 to 17, comprising polymerizing at least one monomer (B1) and optionally an additional monomer, N-vinylpyrrolidone (B2), in the presence of at least one block copolymer backbone (A).

[0136] Embodiment 19 The method according to Embodiment 18, wherein the polymer side chain (B) is obtained by radical polymerization.

[0137] Embodiment 20 The method according to Embodiment 18 or 19, comprising polymerizing at least one monomer (B1) selected from vinyl acetate or vinyl propionate to obtain polymer side chains (B), and optionally at least one further monomer (B2) which is N-vinylpyrrolidone, in the presence of at least one block copolymer backbone (A), a free radical initiator (C), and optionally at least one organic solvent (D) up to 50% by weight based on the sum of components (A), (B1), optionally (B2), and (C), at an average polymerization temperature having a decomposition half-life of 40 to 500 minutes, such that the fractions of unconverted graft monomers (B1) and optionally (B2) and initiator (C) in the reaction mixture are always quantitatively deficient relative to the block copolymer backbone (A).

[0138] Embodiment 21 Use of at least one graft polymer obtained by any one of Embodiments 1 to 17 or by the method described in any one of Embodiments 18 to 21 in laundry detergents, cleaning compositions, and / or fabric and home care products.

[0139] Embodiment 22 Laundry detergents, cleaning compositions, and / or fabric and home care products containing at least one graft polymer obtained by any one of Embodiments 1 to 17 or by the method described in any one of Embodiments 18 to 21.

[0140] Embodiment 23 The laundry detergent, cleaning composition, and / or fabric and home care product according to claim 22, wherein at least one graft polymer is present in an amount ranging from about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5%, relative to the total weight of such composition or product.

[0141] The following examples further illustrate the present invention without limiting its scope. [Examples]

[0142] Measurement of polymers The K value measures the relative viscosity of a dilute polymer solution and is a relative measure of the average molecular weight. For a particular polymer, the K value tends to increase as the average molecular weight of the polymer increases. The K value is determined at a polymer concentration of 1% in a 3 wt% NaCl solution at 23°C, based on the method of H. Fikentscher in "Cellulosechemie", 1932, 13, 58.

[0143] The number-average molecular weight (M) of the graft polymer of the present invention n ), weight average molecular weight (M w ), and polydispersity M w / M nThe molecular weight was determined by gel permeation chromatography in tetrahydrofuran. The mobile phase (eluent) used was tetrahydrofuran containing 0.035 mol / L diethanolamine. The concentration of the graft polymer in tetrahydrofuran was 2.0 mg per mL. After filtration (pore size 0.2 μm), 100 μL of this solution was injected into the GPC system. Four different columns (heated to 60°C) were used for separation (SDV pre-column, SDV 1000A, SDV 100000A, SDV 1000000A). The GPC system was operated at a flow rate of 1 mL per minute. A DRI Agilent 1100 was used as the detection system. Molecular weight M ranged from 10⁶ to 1,378,000 g / mol. n A poly(ethylene glycol) (PEG) standard (PL) containing the specified properties was used for calibration.

[0144] The following (general) procedure was followed using the materials, proportions, and quantities as further shown in Table 1.

[0145] Procedure for Comparative Example 1: Graft polymerization of vinyl acetate onto poly(ethylene glycol) - (Comp.Ex.1) 600 g of poly(ethylene glycol) was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0146] Supply 1, containing 4.8 g of tert-butylperoxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Supply 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Supply 1, Supply 2 (400 g of vinyl acetate) was added and added at a constant rate and at 90°C over 6 hours. Upon completion of Supply 1 and Supply 2, the temperature was raised to 95°C, and Supply 3, consisting of 3.16 g of tert-butylperoxy-2-ethylhexanoate dissolved in 15.70 g of tripropylene glycol, was added at a constant flow rate at 95°C over 56 minutes. Upon completion of the addition of the supply materials, the mixture was stirred at 95°C for 1 hour.

[0147] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour.

[0148] General procedure for non-grafted comparative polymers (Comparative Examples 9-12) 1098.90 g of triblock copolymer, 1.10 g of vinyl acetate, and 58.30 g of 1,2-propanediol were mixed in a polymerization vessel at 90°C and stirred for 3 hours.

[0149] General procedure for graft polymerization of vinyl acetate at a polyalkylene oxide / VAc ratio (60 / 40) 1-(Ex.1, Ex.3~Ex.5, Ex.7, Ex.16, Ex.18~Ex.20; Comp.Ex.2, Comp.Ex.3, Comp.Ex.6) 600 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0150] Supply 1, containing 4.8 g of tert-butylperoxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Supply 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Supply 1, Supply 2 (400 g of vinyl acetate) was added and added at a constant rate and at 90°C over 6 hours. Upon completion of Supply 1 and Supply 2, the temperature was raised to 95°C, and Supply 3, consisting of 3.16 g of tert-butylperoxy-2-ethylhexanoate dissolved in 15.70 g of tripropylene glycol, was added at a constant flow rate at 95°C over 56 minutes. Upon completion of the addition of the supply materials, the mixture was stirred at 95°C for 1 hour.

[0151] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour. The average molecular weight M of the obtained graft polymer (Ex. 7) w The concentration was 5190 g / mol, and the polydispersity was 1.5.

[0152] General procedure 2 for graft polymerization of vinyl acetate at a polyalkylene oxide / VAc ratio (40 / 60) (Ex.2, Ex.6, Ex.14, Comp.Ex.7, Comp.Ex.8) 440 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0153] Feed stock 1, containing 7.97 g of tert-butylperoxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propanediol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed stock 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Feed stock 1, Feed stock 2 (660 g of vinyl acetate) was added and added to the reaction vessel at a constant rate and at 90°C over 6 hours. Upon completion of the feed stock addition, Feed stock 3, consisting of 5.28 g of tert-butylperoxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propanediol, was added at a constant flow rate at 90°C over 56 minutes. Upon completion of the feed stock addition, the mixture was stirred at 90°C for 1 hour.

[0154] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour.

[0155] General procedure 3-(Ex.8, Ex.22, Comp.Ex.4) for graft polymerization of vinyl acetate at a polyalkylene oxide / VAc ratio (70 / 30) 770 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0156] Feed stock 1, containing 7.97 g of tert-butylperoxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propanediol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed stock 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Feed stock 1, Feed stock 2 (330 g of vinyl acetate) was added and added to the reaction vessel at a constant rate and at 90°C over 6 hours. Upon completion of the feed stock addition, Feed stock 3, consisting of 5.28 g of tert-butylperoxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propanediol, was added at a constant flow rate at 90°C over 56 minutes. Upon completion of the feed stock addition, the mixture was stirred at 90°C for 1 hour.

[0157] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour.

[0158] Procedure for graft polymerization of vinyl acetate at a polyalkylene oxide / VAc ratio (90 / 10) - (Ex. 9) 990 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0159] Feed stock 1, containing 7.97 g of tert-butylperoxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propanediol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed stock 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Feed stock 1, Feed stock 2 (110 g of vinyl acetate) was added and added to the reaction vessel at a constant rate and at 90°C over 6 hours. Upon completion of the feed stock addition, Feed stock 3, consisting of 5.28 g of tert-butylperoxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propanediol, was added at a constant flow rate at 90°C over 56 minutes. Upon completion of the feed stock addition, the mixture was stirred at 90°C for 1 hour.

[0160] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour.

[0161] Procedure for graft polymerization of vinyl acetate and vinylpyrrolidone in tripropylene glycol (Ex. 10) 300 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0162] Feed stock 1, containing 6.92 g of tert-butylperoxy-2-ethylhexanoate dissolved in 58.5 g of tripropylene glycol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed stock 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Feed stock 1, Feed stock 2 (180.00 g of vinyl acetate) and Feed stock 3 (120.00 g of vinylpyrrolidone) were added simultaneously and added to the reaction vessel at a constant rate and 90°C over 6 hours. Upon completion of the feed stock addition, the temperature was raised to 95°C, and Feed stock 4, consisting of 1.22 g of tert-butylperoxy-2-ethylhexanoate dissolved in 10.38 g of tripropylene glycol, was added at a constant flow rate at 95°C over 56 minutes. Upon completion of the feed stock addition, the mixture was stirred at 95°C for 1 hour.

[0163] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour. Water (512.40 g) was added.

[0164] Procedure for graft polymerization of vinyl acetate and vinylpyrrolidone in 1,2-propanediol (Ex.11) 376.3 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0165] Supply material 1, containing 7.12 g of tert-butylperpivalate dissolved in 17.01 g of 1,2-propanediol, was administered to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of supply material 1 was administered in the first 10 minutes, and the remainder was administered at a constant rate over 6 hours. Ten minutes after the start of supply material 1, supply material 2 (225.78 g of vinyl acetate) and supply material 3 (150.25 g of vinylpyrrolidone) were simultaneously started and administered to the reaction vessel at a constant rate and at 90°C over 6 hours. Three hours after the start of supply materials 2 and 3, supply material 4 (142.31 g of 1,2-propanediol) was started and administered to the reaction vessel at a constant rate over 3 hours. Upon completion of the raw material supply, the temperature was raised to 95°C, and raw material 3, containing 4.72 g of tert-butyl perpivalate dissolved in 11.25 g of 1,2-propanediol, was administered at a constant flow rate at 95°C over 56 minutes. Upon completion of the raw material addition, the mixture was stirred at 95°C for 1 hour.

[0166] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour. Water (76.84 g) was added.

[0167] Graft polymerization of vinyl acetate and vinylpyrrolidone in tripropylene glycol, followed by partial hydrolysis of the polymerized (previous) vinyl acetate (VAc) units - (Ex. 12) 300 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0168] Feed stock 1, containing 6.92 g of tert-butylperoxy-2-ethylhexanoate dissolved in 58.5 g of tripropylene glycol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed stock 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Feed stock 1, Feed stock 2 (180.00 g of vinyl acetate) and Feed stock 3 (120.00 g of vinylpyrrolidone) were added simultaneously and added to the reaction vessel at a constant rate and 90°C over 6 hours. Upon completion of the feed stock addition, the temperature was raised to 95°C, and Feed stock 4, containing 1.22 g of tert-butylperoxy-2-ethylhexanoate dissolved in 10.38 g of tripropylene glycol, was added at a constant flow rate at 95°C over 56 minutes. Upon completion of the feed stock addition, the mixture was stirred at 95°C for 1 hour.

[0169] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour. Water (512.40 g) was added and the temperature was lowered to 80°C. Sodium hydroxide solution (50%, 68.0 g) was added and the mixture was stirred at 80°C for 60 minutes.

[0170] Procedure for graft polymerization of vinyl acetate and vinylpyrrolidone in 1,2-propanediol, followed by partial hydrolysis of the polymerized (previous) vinyl acetate (VAc) units. (Ex.13) 376.3 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0171] Supply material 1, containing 7.12 g of tert-butylperpivalate dissolved in 17.01 g of 1,2-propanediol, was administered to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of supply material 1 was administered in the first 10 minutes, and the remainder was administered at a constant rate over 6 hours. Ten minutes after the start of supply material 1, supply material 2 (225.78 g of vinyl acetate) and supply material 3 (150.25 g of vinylpyrrolidone) were simultaneously started and administered to the reaction vessel at a constant rate and at 90°C over 6 hours. Three hours after the start of supply materials 2 and 3, supply material 4 (142.31 g of 1,2-propanediol) was started and administered to the reaction vessel at a constant rate over 3 hours. Upon completion of the raw material supply, the temperature was raised to 95°C, and raw material 3, containing 4.72 g of tert-butyl perpivalate dissolved in 11.25 g of 1,2-propanediol, was administered at a constant flow rate at 95°C over 56 minutes. Upon completion of the raw material addition, the mixture was stirred at 95°C for 1 hour.

[0172] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour. Water (76.84 g) was added and the temperature was lowered to 80°C. Sodium hydroxide solution (50%, 67.0 g) was added and the mixture was stirred at 80°C for 60 minutes.

[0173] Procedure for graft polymerization of vinyl acetate with a polyalkylene oxide / VAc ratio (50 / 50) - (Ex.15, Comp.Ex.5) 500 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0174] Feed stock 1, containing 12.24 g of tert-butylperoxy-2-ethylhexanoate dissolved in 50.30 g of tripropylene glycol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed stock 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Feed stock 1, Feed stock 2 (200 g of vinyl acetate) was added and added to the reaction vessel at a constant rate and at 90°C over 6 hours. Upon completion of the feed stock addition, the temperature was raised to 95°C, and Feed stock 3, containing 4.80 g of tert-butylperoxy-2-ethylhexanoate dissolved in 19.70 g of tripropylene glycol, was added at a constant flow rate at 95°C over 56 minutes. Upon completion of the feed stock addition, the mixture was stirred at 90°C for 1 hour.

[0175] The remaining monomer was removed by vacuum distillation at 95°C and 500 mbar for 1 hour.

[0176] Procedure for graft polymerization of vinyl acetate with a polyalkylene oxide / VAc ratio (80 / 20) - (Ex. 17, Ex. 21, Ex. 23) 800 g of triblock copolymer was initially added to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and melted at 90°C.

[0177] Feed stock 1, containing 10.20 g of tert-butylperoxy-2-ethylhexanoate dissolved in 47.61 g of tripropylene glycol, was added to a stirring vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed stock 1 was added in the first 10 minutes, and the remainder was added at a constant rate over 6 hours. Ten minutes after the start of Feed stock 1, Feed stock 2 (200 g of vinyl acetate) was added and added to the reaction vessel at a constant rate and at 90°C over 6 hours. Upon completion of the feed stock addition, Feed stock 3, containing 4.90 g of tert-butylperoxy-2-ethylhexanoate dissolved in 22.39 g of tripropylene glycol, was added at a constant flow rate at 90°C over 56 minutes. Upon completion of the feed stock addition, the mixture was stirred at 90°C for 1 hour.

[0178] The residual monomers were removed by vacuum distillation at 95 °C and 500 mbar for 1 hour.

[0179] Biodegradation test / biodegradability Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. A test substance at 30 mg / mL was inoculated into wastewater collected from the Mannheim wastewater treatment plant and incubated at 25 °C for 28 days in a sealed flask. Using an OxiTop C (WTW), the oxygen consumption during this period was measured as the change in pressure inside the flask. The CO2 released was absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population during biodegradation of the test substance, after correction using a blank, is expressed as a percentage (%) of the ThOD (theoretical oxygen demand).

[0180] The performance evaluation of the graft polymer can be obtained by washing and cleaning experiments. The washing experiment can be carried out in a washing machine or, alternatively, using equipment for performing model washing experiments such as a Launderometer or Tergotometer. To test the anti-redeposition effect, a white fabric was washed together with a soiled fabric in the presence of a detergent composition containing the graft polymer, and the reflectance of the white fabric was determined before and after washing. To test the soil removal effect, a soiled fabric was washed in the presence of a detergent composition containing the graft polymer, and the reflectance of the soiled fabric was determined before and after washing. The dosage of the graft polymer was selected at 0.5 - 5% per weight of the detergent composition. The dosage of the detergent was selected in the range of 1500 - 4500 ppm in the washing liquid. The water hardness (concentration of Ca 2+ and Mg 2+ in the washing liquid) was set to a hardness between 1 - 3 mmol. The washing temperature was selected between 20 °C and 40 °C.

[0181]

Table 1-1

Table 1-2

[0182] Viscosity measurement The viscosity of the sample was measured using a Brookfield viscometer. For measurement, the sample was diluted with tripropylene glycol to obtain the solid content shown in Table 2. The sample was heated to 60°C and measured at 30 rpm using spindle 31.

[0183] [Table 2]

[0184] Whiteness performance in detergents Whiteness performance was tested under the following conditions: Clay dispersion / Whiteness / Clay 3000 ppm / HDL 750 ppm / 25℃ / Hardness 1 mM / Polymer 15 ppm.

[0185] The results are shown in Table 3.

[0186] [Table 3]

[0187] For the whiteness effect test, the following laundry detergent compositions were used, as listed in Table 4:

[0188] [Table 4]

[0189] Test preparation: Prepare the following fabrics for the whiteness effect test: • NA Polyester: PW19, available from Empirical Manufacturing Company (Cincinnati, OH). • Cotton knitted fabric 1: Test fabrics, Inc. 403 Cotton tubular double-sided knitted fabric Available from CW120, Empirical Manufacturing Company (Cincinnati, OH, USA). • Polycotton

[0190] The "washed and FE treated" fabric was prepared according to the following method: 400g of fabric was washed twice in a WE Miniwasher (3.5 liters of water) at 60°C with 18.6g of Ariel® Compact powder detergent on a short-time program (45-minute wash cycle followed by three rinse cycles, total program 90 minutes), twice at 60°C without detergent on a short-time program, and then three times at 40°C with 8.2g of Lenor® Concentrate (fabric enhancer) added to each wash on a short-time program. The fabric was then tumble-dried on a strong dryer until completely dry.

[0191] "Pre-washed" fabric was prepared according to the following method: 400g of fabric was washed twice in a WE Miniwasher (3.5 liters of water) at 60°C with 18.6g of Ariel® Compact powder detergent on a short cycle (45-minute wash cycle followed by three rinse cycles, total program time 90 minutes), and then twice again at 60°C without detergent on a short cycle. The fabric was then tumble-dried on a strong dryer until completely dry.

[0192] Test method: Prepare four types of fabric samples: washed polycotton, washed cotton knit fabric, washed and FE-treated NA polyester, and washed and FE-treated knit fabric.

[0193] Each sample is tested in a 96-well wash system simulator plate, which simulates the agitation of a typical full-scale washing machine using magnetized bearings, under the following conditions: detergent concentration 750 ppm, 150 μL of water per well, 25°C, water hardness 1.0 mM (2:1 Ca+2:Mg+2 molar ratio), wash pH 8.3, and Arizona test dust 3000 ppm (supplied by PTI, Powder Technology Inc).

[0194] Add each polymer listed in Table 5 at 15 ppm in the cleaning solution. Wash each fabric for 60 minutes and dry it in the dark under ambient conditions. For each cleaning condition, there are two 96-well plates, eight internal replicates per 96-well plate, and a total of 16 replicates per cleaning condition.

[0195] Once the samples are dry, for the spots on each 96-well plate, measure L * , a * , b * , and CIE WI using a Spectrolino imaging system (Gretag Macbeth, Spectro Scan 3.273). For each treatment, determine the average CIE WI. Delta CIE WI is the difference in the average CIE WI of the sample relative to the average CIE WI of a control sample without the test polymer, as reported in the subsequent table.

[0196] The whiteness index (WI index) determined for several different fiber materials (see the following table) was calculated as follows:

[0197] "Comparable scaling index" (e.g., as listed) = (total(WI of all fabrics tested with Technology A) × 100) / total(WI of all fabrics tested without technology), and for tests not using the graft polymer in this comparison, set to "100".

[0198] For the whiteness index, use the CIE whiteness index formula, and delta WI was calculated as follows: delta WI of the substrate = WI with technology - WI without technology.

[0199]

Table 5

Claims

1. (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide, and the number of individual blocks (x) in the block copolymer skeleton (A) is an integer, where x is between 3 and 10; and (B) Polymer side chains grafted onto the block copolymer skeleton, wherein the polymer side chains (B) are obtained by polymerization of at least one vinyl ester monomer (B1) and optionally an additional monomer such as N-vinylpyrrolidone (B2); A graft polymer containing [a specific compound / component].

2. It comprises 20–95% by weight of a block copolymer backbone (A) and 5–80% by weight of polymer side chains (B) (relative to the total weight of the graft polymer), The polymer comprises a block copolymer backbone (A) in preferably 40-85% by weight, more preferably 50-80% by weight, and even more preferably 55-75% by weight (relative to the total weight of the graft polymer), and polymer side chains (B) in preferably 15-60% by weight, more preferably 20-50% by weight, even more preferably 20-50% by weight, and even more preferably 25-45% by weight. The graft polymer according to claim 1.

3. The block copolymer skeleton (A) i) obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, or 1,2-butylene oxide, preferably by polymerization of ethylene oxide and 1,2-propylene oxide as monomers, and / or ii) At least one of the two monomers used is ethylene oxide, preferably the second monomer used is 1,2-propylene oxide, and / or iii) The number of individual blocks (x) in the block copolymer skeleton (A) is an integer, where x has a value of 3 to 5, and more preferably x is 3. The graft polymer according to claim 1 or 2.

4. i) The graft polymer has a weight-average molecular weight M of 1,000 to 100,000 g / mol, preferably 2,000 to 45,000 g / mol, and more preferably 3,000 to 30,000 g / mol. w Having, and / or ii) The graft polymer has a polydispersity M in the range of less than 3, preferably less than 2.5, more preferably less than 2.3, and most preferably 1.0 to 2.2 w / M n (M w = weight average molecular weight, M n = number average molecular weight g / mol / g / mol ) and / or iii) The block copolymer skeleton (A) may be capped at one or both of its end groups, preferably the block copolymer skeleton (A) is not capped at both end groups, or if the block copolymer skeleton (A) is capped, the capping is C 1 ~C 25 - Made by alkyl groups and / or iv) The block copolymer skeleton (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). The graft polymer according to any one of claims 1 to 3.

5. The block copolymer skeleton (A) has a structure based on formula (A1) or formula (A2), Equation (A1) is defined as follows: 【Chemistry 1】 (In the formula, n is an integer in the range of 2 to 100, preferably 3 to 80. m is an integer in the range of 2 to 100, preferably 10 to 70, more preferably 14 to 54), or Equation (A2) is defined as follows: 【Chemistry 2】 (In the formula, o is an integer in the range of 2 to 100, preferably 5 to 50, more preferably 8 to 27. p is an integer in the range of 2 to 100, preferably 5 to 50, and more preferably 7 to 24. The graft polymer according to any one of claims 1 to 4.

6. The polymer side chain (B) is obtained by radical polymerization, and / or at least one vinyl ester monomer (B1) is vinyl acetate or vinyl propionate, more preferably vinyl acetate, and / or i) optionally there is an additional monomer, N-vinylpyrrolidone (B2), and / or ii) the polymer side chain (B) is completely or partially hydrolyzed after polymerization, preferably to a maximum of about 50% of the amount of at least one vinyl ester monomer (B1) used in polymerization. The graft polymer according to any one of claims 1 to 5.

7. Polymer side chain (B) (B1) 25 to 100% by weight, preferably 50 to 100% by weight, more preferably 75 to 100% by weight, of at least one vinyl ester monomer (B1) (relative to the sum of (B1) and (B2)), (B2) 0 to 75% by weight, preferably 0 to 50% by weight, more preferably 0 to 25% by weight, of N-vinylpyrrolidone (B2) as a further monomer (relative to the sum of (B1) and (B2) A graft polymer according to any one of claims 1 to 6, obtained by radical polymerization.

8. The polymer side chain (B) is obtained by radical polymerization of at least one vinyl ester monomer (B1) in an amount of 100% by weight (relative to the total amount of monomers used), wherein the vinyl ester monomer (B1) is preferably vinyl acetate or vinyl propionate, and more preferably vinyl acetate. The graft polymer according to any one of claims 1 to 7.

9. Number average molecular weight M of the triblock copolymer skeleton (A) n However, the concentration is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, and even more preferably less than 3000 g / mol, and the weight percentage of vinyl acetate (monomer B) grafted onto the backbone is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50. The graft polymer according to any one of claims 1 to 8.

10. Number average molecular weight M of the triblock copolymer skeleton (A) n However, the concentration is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, even more preferably less than 3000 g / mol, and most preferably less than 2500 g / mol, and the skeleton has structure A2, and the weight percentage of vinyl acetate (monomer B) grafted onto the skeleton is between 10 and 80 (relative to the total weight of the graft polymer), preferably more than 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50. The graft polymer according to any one of claims 1 to 9.

11. A method for obtaining at least one graft polymer according to any one of claims 1 to 10, comprising polymerizing at least one monomer (B1) and optionally an additional monomer, N-vinylpyrrolidone (B2), in the presence of at least one block copolymer skeleton (A), wherein the polymer side chain (B) is obtained by radical polymerization.

12. The method according to claim 11, comprising polymerizing at least one monomer (B1) selected from vinyl acetate or vinyl propionate to obtain polymer side chains (B), and optionally at least one further monomer (B2) which is N-vinylpyrrolidone, in the presence of at least one block copolymer backbone (A), a free radical initiator (C), and optionally at least one organic solvent (D) up to 50% by weight based on the sum of components (A), (B1), optionally (B2), and (C), at an average polymerization temperature having a decomposition half-life of 40 to 500 minutes, such that the fractions of unconverted graft monomers (B1) and optionally (B2) and initiator (C) in the reaction mixture are always quantitatively deficient relative to the block copolymer backbone (A).

13. Use of at least one graft polymer obtained by any one of claims 1 to 10 or by the method described in any one of claim 11 or 12 in laundry detergents, cleaning compositions, and / or fabric and home care products.

14. Laundry detergents, cleaning compositions, and / or fabric and home care products containing at least one graft polymer obtained by the method described in any one of claims 1 to 10 or by the method described in any one of claims 11 or 12.

15. The laundry detergent, cleaning composition, and / or fabric and home care product according to claim 14, wherein at least one graft polymer is present in an amount ranging from about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5%, relative to the total weight of such composition or product.

16. Use of at least one graft polymer in laundry detergents, cleaning compositions, and / or fabric and home care products, wherein the graft polymer is (A) A block copolymer skeleton as a graft base, wherein the block copolymer skeleton (A) is obtained by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide, (B) A polymer side chain grafted onto a block copolymer skeleton, wherein the polymer side chain (B) is obtained by polymerization of at least one vinyl ester monomer (B1) selected from vinyl acetate or vinyl propionate, and optionally an additional monomer, N-vinylpyrrolidone (B2), and Includes, use.

17. A laundry detergent, a cleaning composition, and / or a fabric and home care product comprising at least one graft polymer as defined in claim 16.

18. The laundry detergent, cleaning composition, and / or fabric and home care product according to claim 17, wherein at least one graft polymer is present in an amount ranging from about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5%, relative to the total weight of such composition or product.

Images