DE60014608T2 - Thickened bleach compositions with controlled release and improved viscosity stability at high temperatures - Google Patents

Description

 The The present invention relates to a thickening bleaching composition controlled release, comprising a cross-linked carboxylated Polymer made from ethylenically unsaturated hydrophilic monomers, ethylenically unsaturated hydrophobic monomers and a degradable crosslinking monomer, which has at least two ethylenically unsaturated groups is.

thickened aqueous Bleaching compositions are for formulations for bleach solutions, Disinfectants, cleaning agents for hard surfaces and dishwasher used. The problem with such bleaching compositions however, is that they are subject to degradation and loss of viscosity, which at elevated Temperatures caused by chlorine suffer.

Alkali-soluble polyacrylate and polymethacrylate thickeners for aqueous solutions are well known. However, these have a poor long-term stability in alkaline, oxidative solutions, eg. B. Cleaning formulations containing hypochlorite. EP 0 541 203 describes a hypochlorite bleach-containing gel for dishwashers thickened with cross-linked CARBOPOL-polyacrylic acid. The function of the polyacrylate thickener in the gel is to expand and bind the water. US Pat. 5,348,682 describes a CARBOPOL polyacrylic acid or ACRYSOL ICS-1 (polyEA / MAA) bleach thickening composition. EP 0 636 689 describes a bleaching composition containing a halogen or peroxy bleach material, surfactant and a non-crosslinked polymer. The polymeric thickener is made from a charged hydrophilic monomer and an uncharged hydrophobic monomer. However, one skilled in the art will recognize that this formulation will not have long term stability as measured by accelerated aging assays.

US Pat. 5,169,552 and US Pat. 5,384,061 describe the addition of benzoic acid or its derivatives as radical scavengers to prevent viscosity degradation during accelerated aging by protecting CARBOPOL resins from oxidation by the hypochlorite. US Pat. 4,867,896 describes CARBOPOL analogs which maintain the formulation viscosity solution by reacting the multifunctional sucrose allyl ether and pentaerythritol allyl ester crosslinking agents with crosslinking agents, e.g. As divinylbenzene or 1,2,4-trivinylcyclohexane are replaced, which are relatively inert to degradation by alkaline hypochlorite.

US Pat. 4,839,077 describes the use of mixed systems of surfactants to build up the viscosity of hypochlorite solutions wherein the addition of small amounts of ethylene / acrylic acid polymer causes a synergistic increase in viscosity which is greater than that which can be obtained by thickening the surfactant alone. The polymer has a relatively low molecular weight, is not crosslinked, and has poor solubility, which is due to the presence of surfactants, particularly a non-ionic one such as e.g. As amine oxide, required to be soluble. These formulations have moderate heat aging stability, as shown by a 50% viscosity loss after 4 weeks at 100 ° F.

EP 0 636 691 describes the use of a non-crosslinked styrene-methacrylic acid polymer to thicken hypochlorite / surfactant solutions wherein crosslinking of the polymer provides higher viscosity but reduces clarity of the solution. These thickened solutions lack long-term stability, losing 50% of their viscosity after 6 weeks at room temperature.

Out these reasons there is a continuing need for thickening bleach compositions, the thickening effect even at temperatures near 48.9 ° C (120 ° F) for 3 to Maintained for 4 weeks.

A thickening controlled release bleach composition comprising bleach, water and 0.1 to 50% by weight, based on the total weight of the thickening bleach composition, of at least one crosslinked, carboxylated polymer, which comprises from 30 to 80% by weight of at least one ethylenically unsaturated hydrophilic monomer, 20 to 70% by weight of at least one ethylenically unsaturated hydrophobic monomer and about 0.5 to about 10% by weight of a degradable crosslinking monomer selected from the group consisting of a crosslinking monomer containing at least two ethylenically unsaturated moieties has prepared a crosslinking monomer having at least one ethylenically unsaturated group and at least one functional group capable of reacting with another functional group on a monomer to form a degradable crosslinking, and combinations thereof, wherein the weight percent on the total weight of the monomer , which helps to connect the ver nested carboxylated polymer is used.

In the thickening bleach composition with controlled Release according to the invention the solubility of the polymer is suppressed by crosslinking. Most of the polymer is isolated from degradation by the bleach, creating a Degradation of the polymer backbone, which reduces the molecular weight and destroyed the thickening effect, is prevented. A slower but selective degradation of polymer crosslinks acts such that a small amount of polymer that acts as an effective Thickener acts, is solubilized. Once it is soluble, the polymer backbone is slowly degraded by the bleach. A continuous feed of the soluble Polymer is developed by this time release mechanism, so that the soluble Polymer is replenished when degraded by the bleach , whereby the thickening effect after aging at elevated temperature much longer is maintained as it used to be the art has been shown.

Around one over longer Time consistent viscosity To obtain, it is advantageous to use a mixture of polymers with different To have quantities or types of crosslinking agents. So deliver easily crosslinked polymers have an initial viscosity, while highly crosslinked polymers less soluble and provide long-term reserves that released more slowly become.

Short description the drawings

The The above and other features of the invention will become apparent in the following detailed description, taken in conjunction with the accompanying drawings is seen, closer described; from the drawings is:

1 a graph showing the viscosity vs. Time of two polymers in a commercial detergent composition containing sodium hypochlorite without synergistic polymer / soap interactions;

2 a graph showing the viscosity vs. Shows time for four polymers in a 2% sodium hypochlorite solution without detergents;

3 a graph showing the viscosity vs. Polymer percent in a detergent composition containing sodium hypochlorite with synergistic polymer-soap interactions;

4 a graph showing the viscosity vs. Time of three polymers in a 2% sodium hypochlorite / 1% amine oxide / 1% sodium lauryl ether sulfate solution shows.

The Thickening bleach composition with controlled release the invention contains bleach, Water and a cross-linked, carboxylated polymer. The networked Polymer is made by emulsion or solution polymerization. The crosslinked polymer is in an amount of 0.1 to 50 wt .-%, preferably 1 to 25 wt .-%, more preferably 2 to 10 wt .-%, based on the total weight the thickening bleach composition with controlled Release, before. The term "gradient-crosslinked" as used herein means that the carboxylated polymer in contrast to a "homogeneous crosslinking" has different degrees of crosslinking. Thus, the polymers become dependent on the degree of cross-linking at different times in a bleaching composition soluble.

The crosslinked polymer is from 30 to 80 wt .-% of at least one ethylenic unsaturated hydrophilic monomer, 20 to 70 wt .-% of at least one ethylenic unsaturated hydrophobic monomer and about 0.5 to about 10% by weight of a degradable crosslinking monomer produced, wherein the weight percent on the total monomer weight, that for the production of the polymer is used. As used herein, the term "degradable crosslinking monomer" means that the linkages formed by the crosslinking of the monomer are capable by alkaline hydrolysis or by reaction with bleach to be disconnected. An example of a reduction in networking is the alkaline hydrolysis of polymerized esters, eg. B. ethylene glycol dimethacrylate or diallyl maleate forming the crosslink. Preferably the polymer consists of 50 to 70% by weight of at least one hydrophilic monomer, 30 to 50 wt .-% of at least one hydrophobic monomer and about From 1 to about 5 weight percent of a degradable, crosslinking monomer.

The degradable crosslinking monomer is a crosslinking monomer having at least two ethylenically unsaturated moieties, or a crosslinking monomer having at least one ethy and at least one functional group capable of reacting with another functional group on a monomer to form a degradable crosslinking. It is within the scope of the invention that the degradable crosslinking is formed in situ or after polymerization of the ethylenically unsaturated hydrophilic monomer and the ethylenically unsaturated hydrophobic monomer. Glycidyl methacrylate contains z. An epoxide ring capable of reacting with methacrylic acid such that the polymer of the invention can be polymerized at low temperature and the temperature for activating crosslinking can be increased. The result is an ester linkage which is readily degradable by alkaline hydrolysis. It is also possible to use combinations of degradable crosslinking monomers.

The polymers of the invention can be crosslinked by any optional chemical linkage, although the following types of linkage or linkage are preferred:

Preferably The degradable crosslinking monomer is made from esters of acrylic acid, esters of methacrylic acid, Esters of maleic acid, Esters of crotonic acid, Esters with allyl or methallyl alcohol, allyl ethers or vinyl ethers of polyethylene glycol, allyl sucrose ethers, thioesters, thioamides, unsaturated epoxides, Isocyanates and silanes selected. Specific examples of Crosslinking monomers are glycidyl methacrylate, 2-isocyanatoethyl methacrylate, α, α-dimethylmeta-isopropenylbenzyl isocyanate, Vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, ethylene glycol dimethacrylate, Polyethylene glycol diacrylate, butanediol diacrylate, pentaerythritol tetraacrylate, Trimethylolpropane triacrylate, diallyl phthalate, diallyl maleate, allyl methacrylate, Vinyl crotonate, triallyl cyanurate, diallyl phosphate, ethanedithiodiacrylate, N-methylolacrylamide and N, N'-methylene-bis-acrylamide. Most advantageously, the degradable crosslinking monomer is diallyl maleate or ethylene glycol dimethacrylate.

The crosslinked polymer is prepared from at least one ethylenically unsaturated hydrophilic monomer selected from acids, preferably C ₁ -C ₆ acids, amides, ethers, alcohols, aldehydes, ketones and esters. Preferably, the ethylenically unsaturated hydrophilic monomers are monounsaturated. Combinations of ethylenically unsaturated hydrophilic monomers can also be used. Preferably, the ethylenically unsaturated hydrophilic monomers are sufficiently water-soluble to form at least a 5% by weight solution in water.

specific examples for ethylenically unsaturated hydrophilic monomers are acrylic acid, methacrylic acid, ethacrylic, alpha-chloro acrylic acid, alpha-cyanoacrylic acid, beta-methylacrylic acid (crotonic acid), alpha-phenylacrylic acid, beta-acryloxypropionic acid, sorbic acid, alpha-chlorosorbic acid, angelicic acid, cinnamic acid, p-chlorocinnamic acid, beta-styrylacrylic acid (1-carboxy-4-phenylbutadiene-1,3), Itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxyethylene, 2-acryloxy propionic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, 2-hydroxyethyl acrylate, Sodium methallylsulfonate, sulfonated styrene, allyloxybenzenesulfonic acid, dimethylacrylamide, dimethylaminopropyl methacrylate, Diethylaminopropyl methacrylate, vinylformamide, vinylacetamide, polyethylene glycol ester of acrylic acid and methacrylic acid and itaconic acid, Vinylpyrrolidone and vinylimidazole. Preferably, the ethylenic unsaturated hydrophilic monomer selected from methacrylic acid or acrylic acid.

The crosslinked polymer is at least one ethylenically unsaturated hydrophobic monomer produced. Preferably, less will be than 20 g / l, more preferably less than 5 g / l, most preferably less than 1 g / L of the hydrophobic monomer in water at ambient temperature and a pH of 3.0 to 12.5. Preferably, the ethylenically unsaturated hydrophobic monomer is unsaturated Alkyl and alkoxy chains, e.g. B. with 5 to 24 carbon atoms, preferably 6 to 18 carbon atoms, most preferably 8 to 16 carbon atoms, selected. It can also combinations of hydrophobic monomers can be used.

Specific examples of ethylenically unsaturated hydrophobic monomers are styrene, α-methylstyrene, 2-ethylhexylacrylate, octylacrylate, laurylacrylate, stearylacrylate, behenylacrylate, 2-ethylhexylmethacrylate, octylmethacrylate, laurylmethacrylate, stearylmethacrylate, behenylmethacrylate, methylmethacrylate, ethylacrylate, 2-ethylhexylacrylamide, octylacrylamide, laurylacrylamide, stearylacrylamide, behenylacrylamide, propylacrylate, butylacrylate, pentylacrylate, nexylacrylate, 1 Vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and 4- (phenylbutyl) styrene. A preferred hydrophobic monomer is styrene.

The Bleaching agent used in the thickening bleach compositions used with controlled release is different from Halogen bleach selected. examples for such bleaching agents include the alkali metal and alkaline earth metal salts of hypohalite, haloamines, haloimines, haloimides and Haloamides. A preferred hypohalite is hypochlorite and Compounds that are in aqueous solution Produce hypochlorite. Suitable hypochlorite-producing compounds include sodium, potassium, lituium and calcium hypochlorite, chlorinated Trisodium phosphate dodecahydrate, potassium and sodium dichloroisocyanurate and trichlorocyanuric acid. Organic bleach sources suitable for use include heterocyclic N-bromo and N-chloro imides, e.g. B. trichlorocyanuric acid and tribromocyanuric, Dibromo and dichloro cyanuric acid and potassium and sodium salts thereof, N-brominated and N-chlorinated Succinimide, malonimide, phthalimide and naphthalimide. Also suitable are hydantoins, z. B. Dibromo- and Dichlorodimethylhydantoin, Chlorbromdimethylhydantoin, N-chlorosulfamide (Haloamide) and chloramine (haloamine). Particularly preferred Sodium hypochlorite with the formula NaOCl in an amount in the range from about 0.2% to about 15% by weight, more preferably about 0.2 Wt% to about 10 wt%, and most preferably from about 1% to about 5%.

In an embodiment of the invention are the thickening bleach compositions with controlled release or sustained release for thickening structured solutions surfactants Agents containing halogen bleach can be used. Such structured solutions surfactants Agents contain surface-active High concentration agents to achieve a certain viscosity, typically of the order of magnitude from 50 to 1,000 cps. A polymeric thickener may be added be to the amount of surface-active Reduce funds needed will be to the desired viscosity or to increase the viscosity above the value with concentrated surface active Means alone can be obtained. In addition, that may be present of soluble Polymer adversely affects the interactions of the surfactant influence and lead to a decrease in viscosity. To be enough polymer into a structured soap / bleach solution for long-term viscosification It is preferred to load the polymer solubility by degradable crosslinking to suppress.

The Thickening bleach composition of controlled composition may optionally be surface-active Contain agent and / or clay as a viscosity enhancer, which has a synergistic thickening effect with the crosslinked provide carboxylated polymer. The surfactants and / or clays are preferably opposite a degradation by the bleach resistant. Suitable surface-active Agents include nonionic, anionic, cationic and amphoteric surfactants Medium. Suitable surface-active Funds for the thickening bleach compositions to the controlled Release include soaps. The surfactants are optionally in an amount of about 0 to about 50% by weight, preferably about From 2 to about 45% by weight, and more preferably from about 5 to about 40% by weight of thickening bleach composition with controlled release in front.

Anionic surfactants include e.g. C ₈ -C ₁₂ alkyl benzene sulfonates, C ₁₂ -C ₁₆ alkane sulfonates, C ₁₂ -C ₁₆ alkyl sulfates, C ₁₂ -C ₁₆ alkyl sulfosuccinates or sulfated ethoxylated C ₁₂ -C ₁₆ alkanols.

Nonionic surfactants include e.g. As C ₆ -C ₁₂ alkylphenol ethoxylates, C ₁₂ -C ₂₀ alkanol alkoxylates and block polymers of ethylene oxide and propylene oxide. Optionally, the end groups of polyalkylene oxides may be blocked, whereby the free OH groups of the polyalkylene oxides may be etherified, esterified, acetalated and / or aminated. Another modification consists in the reaction of the free OH groups of the polyalkylene oxides with isocyanates. The nonionic surfactants also include C ₄ -C ₁₈ alkyl glucosides as well as the alkoxylated products obtainable therefrom by alkoxylation, especially those obtainable by reaction of alkyl glucosides with ethylene oxide.

cationic surfactants Means contain hydrophilic functional groups, where the charge the functional group is positive if these are in an aqueous solution solved or dispersed. Typical cationic surfactant Means include, for. As amine compounds, oxygen-containing amines and quaternary Amine salts.

amphoteric surfactants Agents contain both acidic and basic hydrophilic groups. amphoteric surfactants Agents are preferably derivatives of secondary and tertiary amines, Derivatives of quaternary Ammonium, quaternary Phosphonium or tertiary Sulfonium. The cationic atom in the quaternary compound may be part of a heterocyclic ring. The amphoteric surfactant Contains funds preferably at least one aliphatic group containing about 3 to contains about 18 carbon atoms. At least one aliphatic group preferably contains an anionic, in water solubilizing group such as. As carboxy, sulfonate or Phosphono.

in the general are anionic surfactants, e.g. B. linear Alkyl sulfonates (LAS), e.g. As sodium lauryl ether sulfate, or non-ionic surfactants Means, e.g. Amine oxides, for example AMMONYX L0 and AMMONYX MO, available from Stepan Chemical Company, and acyl sarcosinates, e.g. B. HAMPOSYL-L (n-lauroylsarcosine), available from Hampshire Chemical Company, for use in thickening bleaching compositions with controlled release preferred.

The thickening bleach compositions with controlled release can optionally contain an electrolyte. Low concentrations to electrolytes, eg. As sodium chloride, act such that they are ions in water solution and have been shown to improve solution viscosity. Sodium chloride is generally in sodium hypochlorite, as well as it is available in stores is, present or may be of the composition in suitable amounts be added so that the stability of the sodium hypochlorite is not adversely affected.

The Thickening bleach composition with controlled release may optionally also contain a buffer to maintain the pH. Alkaline pH's, typically between 11 and 14, for example about 13, are generally suitable for achieving a desired viscosity and stability. Some reagents function as both an electrolyte and a buffer.

The thickening bleach compositions with controlled release can as well at least include an additive. Suitable additives may, for. B. dye transfer inhibitors, Anti-corrosion materials, antistatic agents, optical brighteners, perfumes, Perfumes, dyes, fillers, Chelating agent, tissue dehumidifier, brightening agent, Foam control agents, buffers, soil release agents, fabric softeners and Combinations of these include. In general, such additives and their amounts are known to those skilled in the art.

Without to tie themselves to a particular theory, go the inventors of the present invention, that in the thickening bleach compositions controlled-release solubility of the crosslinked emulsion polymer so suppressed that will be the polymer first minimal, if any, the bleaching solution thickened. However, if the alkaline bleach solution is the decomposes crosslinked groups of the polymer solubilizes the crosslinked polymer gradually and thicken the bleach solution. Preferably, the rate of solubilization of the polymer in the bleach solution is greater than or equal to equal to the rate at which the bleach degrades the soluble polymer.

If it is necessary to have a crosslinked polymer with suppressed solubility to have high polymer concentrations, it is sufficient to polymer to save the release over time. To be consistent Viscosity over the To obtain time, it is advantageous to use a mixture of polymers with different amounts or types of crosslinking agents to have. Thus, slightly crosslinked polymers provide initial viscosity while high crosslinked polymers less soluble and provide long-term reserves that released more slowly become.

The The following nonlimiting examples illustrate further aspects of the invention. Unless otherwise indicated in the following examples, the following was added the viscosity the solution determined using a Brookfield viscometer at 25 ° C.

example 1

Comparative Example - not crosslinked polymer

PPE-1196 is a non-crosslinked alkali-soluble emulsion polymer which contains about 46% styrene and 54% methacrylic acid and is from National Starch and Chemical Company available. The polymer has a solids content of 30%.

Example 2

manufacturing a homogeneously crosslinked carboxylated polymer

One 1 liter four-necked reaction vessel with a stirrer, a thermometer, a catalyst addition funnel, a device to build up a nitrogen blanket and a pump for monomer transfer from a continuously stirred container fitted. An initial charge, the 300 g of water, 3.0 g of sodium dodecylbenzenesulfonate and 0.1 g of 2-acrylamido-2-methylpropanesulfonic acid, was prepared and after the nitrogen purge was complete, the initial charge became placed in the vessel and with continuous stirring while the reaction to 80 ° C heated. While the container under a nitrogen atmosphere was held, was a monomer emulsion consisting of 300 g Water, 2.5 g of sodium dodecylbenzenesulfonate, 150.0 g of styrene, 65.0 g methacrylic acid, 65.0 g of acrylic acid, 0.5 g of 2-acrylamido-2-methylpropanesulfonic acid, 4 g of ethylene glycol dimethacrylate and 10.0 g of behenyl (25) -POE-itaconate 1/2 ester. In the monomer mix tank was maintained by constant mixing emulsification.

A initiator solution was prepared by adding 0.9 g of sodium persulfate in 125 g of water were used. A portion of the monomer emulsion, 30 g, was added in the heated Given vessel. After 5 minutes, 35 g of the persulfate solution was added and the contents of the vessel was allowed to react for 10 minutes. Then the remaining monomer emulsion was passed over a 3 hours, with the remaining persulfate solution simultaneously over 3 1/2 Hours were added.

To Termination of the monomer feed became the latex with a solution containing 0.5 g of 70% tert-butyl hydrogen peroxide in 11.0 g of water, intercepted with a single shot. Once the persulfate solution was complete, became a scavenger solution, the 0.7 g of erythorbic acid in 11.0 g of water, over Added for 15 min. The latex was kept at 80 ° C for 30 minutes, at 40 ° C chilled and filtered to remove formed coagulant. It was determined, the filtered latex had a solids content of 27.5%.

Example 3

manufacturing a homogeneously crosslinked carboxylated polymer

One Polymer was prepared by the method set forth in Example except that 7.0 g of ethylene glycol dimethacrylate was used. The solids content of the filtered latex was determined to be 28.4%.

The polymers prepared in Examples 1 and 3 were evaluated in CLOROX CLEANUP, a commercial detergent composition containing 1.9% by weight sodium hypochlorite and a small amount of surfactant. This solution was thickened with either 2.5% of the thickener of Example 1 containing no crosslinking agent or 4.9% of a highly crosslinked alkali-soluble emulsion of Example 3. Upon addition of the polymer, the pH of the solution was increased to about 12.5 and the polymer samples were stored at 50 ° C for up to 3 weeks. The test results are shown in Table I and in 1 summarized.

Table I

The test results in Table I show that a conventional, non-crosslinked, alkali-soluble emulsion thickener (Example 1) in a hypochlorite bleach formulation degrades rapidly and loses its viscosity while a highly cross-linked sustained release polymer (Example 3) is capable of the solution itself after 3 weeks at 50 ° C, which simulates aging over several months to thicken. The Diagram shows that the non-crosslinked polymer of Example 1 was completely degraded in 7 days. However, even after 21 days, the crosslinked polymer of Example 1 further thickened the detergent composition.

Example 4

manufacturing a homo crosslinked carboxy-polymer

One Polymer was prepared according to the method described in Example 2, except that the following amounts of reactants differ in the monomer mixture were 132.0 g of styrene, 74.0 g of methacrylic acid and 74.0 g of acrylic acid, 10.0 ethylene glycol dimethacrylate and 14.0 g of behenyl (25) -POEitaconsäure-1/2-ester, prepared. It was found that the solids content of the filtered Latex was 25.7%.

Example 5

manufacturing a gradient-crosslinked carboxylated polymer

One 1 liter four-necked reaction vessel with a stirrer, a thermometer, a catalyst addition funnel, a device to build up a nitrogen blanket and a pump for monomer transfer a continuously stirred container fitted. An initial load was prepared, the 390.66 g of water, 8.82 g of CRODAFOS N3A, 13.81 g of RHODASURF LA-3 and 3.37 g a 0.910 molar ammonia solution contained. As the nitrogen purge was finished, the initial feed was added to the jar and at 65 ° C heated. While the vessel under nitrogen atmosphere was held, was a monomer emulsion consisting of 215.54 g of water, 8.82 g CRODAFOS N3A, 13.81 g RHODASURF LA-3, 74.90 g styrene, 165.36 g of methacrylic acid, produced. Emulsification was by constant mixing in the monomer mix tank maintained.

Three equivalents Doses of crosslinker, diallyl maleate, each at 1.81 g produced. An initial catalyst solution containing 0.20 g of sodium persulfate in 16.84 g of water was prepared. The beginning monomer mix from 8.62 g of styrene and 12.12 g of methacrylic acid was prepared. The Initial monomer mixture was added to the heated initial charge and mixed for 5 minutes. Next became the initial catalyst added and the reaction was stirred while the reaction temperature at 80 ° C elevated was and then for 15 min at 80 ° C was held. The remaining monomer emulsion was over a 4 hours added during an addition of 1.81 g Diallyl maleate was added to the monomer mix tank when 1/4, 1/2 and 3/4 of the monomer emulsion had been added to the reaction vessel. A slow one Adding a persulfate solution, which consisted of 0.27 g of persulfate and 60.62 g of water was carried out simultaneously over 4 1/2 Hours.

To Termination of the monomer feed was the latex with a solution of 0.07 g of sodium persulfate in 20.21 g of water, which in the course of 1 Hour was added, intercepted. The latex was cooled to 40 ° C and filtered to remove a formed coagulant. It was determined, the filtered latex has a pH of 2.43 and a solids content of 30.5% and an average particle size of 161 nm.

Example 6

manufacturing a gradient-crosslinked carboxylated polymer

To the method described in Example 5, except that 2.25 g of diallyl maleate were added to the monomer mix tank as 1/4, 1/2 and 3/4 of the Monomer emulsion were introduced into the reaction vessel, a Polymer produced. It was found that the filtered Latex had a solids content of 30.6%.

Example 7

manufacturing a gradient-crosslinked carboxylated polymer

Following the procedure described in Example 5, except that 3.05 g of diallyl maleate was added to the monomer mix tank when 1/4, 1/2 and 3/4 of the monomer emulsion was introduced into the reaction vessel, a polymer was prepared. The filtered latex was found to have a solids content of Had 30.6%.

Example 8

manufacturing a gradient-crosslinked carboxylated polymer

It is an initial charge containing 391 grams of water, 9.4 grams of CRODAFOS N3A, 13.9 g of RHODASURF LA-3 and 3.4 g of a 0.910 molar ammonia solution. After the rinse was finished with nitrogen, the initial feed was in the Given vessel and at 65 ° C heated. While the vessel under a nitrogen atmosphere was a monomer emulsion consisting of 215 g of water, 8.6 g of CRODAFOS N3A, 13.8 g of RHODASURF LA-3, 79.30 g of styrene, 171.45 g methacrylic acid, produced. Emulsification was by constant mixing in the monomer mix tank maintained. There were three equivalent doses of a mixture each prepared from 1.02 g of ethylene glycol dimethacrylate and 1.02 g of diallyl maleate.

A Initial catalyst solution containing 0.2 g of sodium persulfate in 16.8 g of water was prepared. It An initial monomer mixture was prepared from 4.3 g of styrene and 6.05 g of methacrylic acid. The initial monomer mixture was added to the heated initial charge and mixed for 5 minutes. Next became the initial catalyst added and the reaction was stirred while the reaction temperature at 80 ° C elevated was and then for 15 min at 80 ° C was held. It should be initiated a polymerization and was a change visible at the solution opacity. Residual monomer emulsion was over a period of 3 hours, with an addition of 2.04 g of the diallyl maleate / ethylene glycol dimethacrylate mixture in the Monomer mixing tank took place when 1/4, 1/2 and 3/4 of the monomer emulsion been led into the reaction vessel were. At the same time, a slow addition of a persulfate solution, the composed of 0.27 g of persulfate and 60.6 g of water, over time from 3 1/2 hours. Upon completion of the monomer addition, the reaction became a solution of 0.1 g of 70% tert-butyl hydrogen peroxide in 2.0 g of water. After completion of the catalyst addition was a scavenger of 0.1 g of erythorbic acid in 10 g of water over time added for 30 min. The latex was cooled to 40 ° C and filtered to form coagulant to remove. It was found that the filtered latex had a Had solids content of 30.0%.

Example 9

manufacturing a gradient-crosslinked carboxylated polymer

To the method described in Example 8, except that the following amounts used in the slow monomer addition: 150.0 g of methacrylic acid and 100.0 g of styrene, a polymer was prepared. It was determined, the filtered latex had a solids content of 29.8%.

Example 10

The in Examples 5, 8 and 9 produced polymers were in a aqueous Solution, the 1.9% sodium chloride, 2.9-3.7% polymer and about 1 g sodium hydroxide solubilized per 1 g of dry polymer, then the pH increased to 13.0 with sodium hydroxide. The solutions were stored at 50 ° C. The test results are summarized in Table II.

Table II

The results in Table II show that even after 21 days, the polymers of the present invention continue to thicken alkaline aqueous solutions. The alkalinity of the solution selectively degrades the polymer crosslinking agent, which suppresses polymer solubility, but does not degrade the polymer backbone to reduce viscosity. The results also show that the higher the polymer concentration in the alkaline Solution is, the stronger the thickening effect.

Example 11

Alkali-soluble emulsion polymers were in an aqueous solution with 50 ° C, 1 to 3% sodium hypochlorite, 3.0 to 3.5% polymer, and approximately 1 g of sodium hydroxide per g of dry polymer, solubilized, then the pH was raised to 13.0 with sodium hydroxide. The solutions were at 50 ° C stored. The test results are summarized in Table III.

Table III

The Results in Table III show that higher bleach concentrations compared to lower levels of bleach the Break down polymers faster. However, keep the polymers of the invention the thickening effect on the bleaching solution is maintained much longer as the non-crosslinked polymer prepared in Example 1. The polymer of Example 1 without crosslinker is fast after 7 days from 2020 cps to 476 cps. The crosslinked polymer of Example 5 has an initial viscosity of 1336 cps, holds but his time-delayed Effect still over 7 days in 1% sodium hypochlorite upright. The results in table III also show that the polymer of Example 5 does not contain enough crosslinking agent to form a To enable long-term release so the viscosity steadily decreasing after 7 days.

Example 12

The alkali-soluble emulsion polymers prepared in Examples 2, 7, 8 and 9 were solubilized in aqueous solutions containing 1 to 3% sodium hypochlorite, 3.0 to 3.5% polymer and about 1 g of sodium hydroxide per g of dry polymer the pH is raised to 13 with sodium hydroxide. The solutions were stored at 50 ° C. The test results are summarized in Tables IV, V and VI. 2 is a graphical representation of the results in Table V.

Table IV

Table V

Table VI

The Results in Tables IV, V and VI show that the polymers of the invention even after 21 days at 50 ° C a 1 to 3% bleach solution continue to thicken. The homogeneous polymer of Example 2 had its initial viscosity the strongest suppressed it quickly hydrolyzed and reached its peak viscosity, followed by from a rapid drop in viscosity. This behavior is poor when the bleach content increases. The gradient crosslinked polymers have better performance, since the lightly crosslinked components provide an initial viscosity, while the higher networked and more resistant to hydrolysis Fractions reserves for provide a slow sustained release.

To 21 days at 50 ° C contained 3% bleach samples with polymer still on average 47% of the original Bleach content. The 2% bleach samples with polymer contained 41% of the original amounts and the 1% bleach samples with polymer contained on average 35% of the original amount. Of some of the surface active Alkylethoxylate agents that are present in polysynthesis are known to they cause bleaching degradation and it is believed that's why a fixed amount of bleach loss proportional to the amount of the added emulsion polymer.

It it is emphasized that alkaline conditions are not the sole responsibility of the polymer reduce, but that the viscosity decrease from a polymer decomposition caused by bleach, result.

Example 13

manufacturing a homogeneously crosslinked carboxylated polymer

One Polymer was prepared by the method described in Example 2, except that the ethylene glycol dimethacrylate crosslinking agent from the recipe was excluded. It was determined that the filtered latex had a solids content of 26.8%.

The polymers prepared in Examples 2, 3 and 13 were added to Comet Gel, which is a concentrated surfactant / bleach detergent product having a viscosity of about 500 cps. The polymers were evaluated for their synergistic thickening effect at various concentrations in the comet gel. The test results are summarized in Table VII. 3 is a graphic Presentation of Table VII.

Table VII

The Results in Table VII show that the polymer of Example 13, that does not contain a degradable crosslinking agent at a concentration from 0.5 and 1.1 a large one viscosity increase causes at higher Concentrations of 1.5 and 2.2 the polymer with the structuring of the surface-active By means of interacts and causes the viscosity even below the viscosity of 478 cps of solution lowers without polymer. The polymer of Example 2 is equivalent cross-linked and although there is a peak in viscosity, Much more polymer can be added without changing the formulation viscosity to the viscosity of the solution without the polymer falls off. The polymer of Example 3 has more suppressed its solubility than the polymer of Example 2; In this way, high concentrations of this Polymers for one Thickening effect that over an even longer one Period is released, to be added.

Example 14

evaluation of polymers prepared in Example 1 and Example 4 were in thickening bleach compositions during one accelerated aging storage at 50 ° C (122 ° F).

The Cross-linked carboxylated polymer prepared in Example 4, 4.1 g, was reacted with 20 g RHODAPEX ES-2 (a 25% solution of 2 mol% ethylene oxide lauryl ether sulfate as a surface-active Medium) ("SLES"), 67 g distilled Water, 4 g sodium hydroxide and 100 g liquid bleach CLOROX (approx 5.4% sodium hypochlorite). This resulted in a 2.5% bleach solution, the by the interaction of 2.5% of the surfactant and 0.53% crosslinked polymer was thickened. The solution had an initial viscosity of 330 cPs and contained 2.5% sodium hypochlorite in the analysis. The pH was determined to be 13.0. The solution was as a result of insoluble crosslinked polymer cloudy.

The Polymer of Example 1 containing a crosslinking agent became under similar Conditions assessed, except 2.9% RHODAPEX ES-2 was used and less polymer required was. The test results are summarized in Table VIII.

Table VIII

The test results in Table VIII show that the polymer of Example 4 prepared according to the invention further thickened the thickening bleach composition for up to 3 weeks. After 22 days, the sodium hypochlorite content was 1.4%. The test results also show that the non-crosslinked polymer prepared in Example 1 was unacceptable because the bleaching solution was left over the first 13 days Total viscosity was lost.

Example 15

manufacturing a thickening bleach composition

A 2% sodium hypochlorite solution containing a mixed surfactant system was prepared by mixing 75 g of Clorox Bleach (about 5.4% sodium hypochlorite), 2.15 g of sodium hydroxide, 97 g of distilled water, 7.5 g of RHODAPEX ES. 2 (25% active) and 6.5 g AMMONYX MO (30% active) were mixed. This solution typically gave a viscosity of 75-150 cps. To 60 g of this solution was added 1.1 g of the emulsion polymer in Example 5 (30% solids). The pH of the mixture was adjusted to 13.0 and the viscosity was increased to 310 cps. The sample was placed in a 50 ° C oven and periodically removed to examine the viscosity and hypochlorite content. This procedure was used to prepare samples with polymers from Examples 1, 5 and 7. The test results are summarized in Table IX. 4 is a graphical representation of Table IX.

Table IX

The Test results in Table IX show that the polymer in Example 1 without crosslinking agent was rapidly degraded and the mixture after 10 days the total viscosity had lost. The crosslinked polymers initially increased in viscosity then a suitable viscous solution while of the 3 to 4 week trial period. After 21 days was the Hypochlorite content 0.91% for the formulation with the polymer of Example 5 and 0.63% for the polymer from Example 7 after 27 days.

Example 16

manufacturing a thickening bleach composition

Comet Gel is a commercially available one thickened bleach composition containing about 0.9-1% sodium hypochlorite and thickened with bleach-stable surfactants is, leaving a viscosity of 500 cPs is achieved. The viscosity of the Comet gel was through Addition of 0.5 to 0.8% (dry basis) of the polymer thickener of Examples 5 and 8, to a viscosity of 1000 cps at a pH of 12.8 to 13, with 50% sodium hydroxide was set to reach. The samples were for 3 weeks at 50 ° C stored. The test results are summarized in Table X.

Table X

The test results in Table X show that the polymer of Example 8 has the viscosity at about 1000 cPs was constant for 3 weeks while the polymer of Example 5 resulted in a constant increase in viscosity. In this way, the polymer of Example 5 was solubilized faster than it was degraded. It was also determined that 80% of the original amount of hypochlorite remained after 21 days.

Example 17

manufacturing a thickening bleach composition

Of the Bleach content of the comet gel was increased to 2.3% by 40 g Comet gel with 18 g Clorox bleach (5.4% sodium hypochlorite) resulting in a mixture having a viscosity of 330 cPs led. The mixture was mixed with 0.5% (dry basis) of the polymer thickener Examples 5 and 6 formulated with a viscosity of 800 to 1000 cps at a pH of 12.8 to 13, adjusted with 50% sodium hydroxide had been received. The test results are in Table XI summarized.

Table XI

The Test results in Table XI show that the highly crosslinked polymers Examples 5 and 6 were compatible and produced homogeneous mixtures, the one viscosity near the target area for 4 weeks at 50 ° C kept upright before it decreased. The high bleach concentration The polymer of Example 5 degraded rapidly enough that the viscosity after the first week was kept almost constant. It was determined, that 56% of the original Bleach content was maintained after 21 days.

Example 18

Effect of a non-degradable crosslinking agent

One Polymer was prepared according to the procedure described in Example 9, except that the ethylene glycol dimethacrylate and diallyl maleate crosslinking agent was replaced by 0.63 g of divinylbenzene which homogeneously with the monomer was mixed slowly added at the beginning of the reaction was produced. It was found that the filtered latex had a solids content of 30.0%.

It became an alkaline solution prepared at pH 13.0 containing 0.6 g of the polymer of Example 18, which contained divinylbenzene which was a non-degradable crosslinking agent is 100 g of 2% sodium hypochlorite and 3 g of 50% sodium hydroxide contained. It became a separate alkaline solution with pH 13.3 from 11.6 g of the polymer of Example 18, 145 g of distilled water, 5 g of 50% strength Sodium hydroxide and 3 g of sodium chloride. The test results are summarized in Table XII.

Table XII

The Test results in Table XII show that the viscosity of the polymer of Example 18 in alkaline solution without bleach, only about 30% increased after the first week had, indicating that the polymer crosslinks to hydrolysis were stable. In comparison, the degradable crosslinks produced in Example 10, a 10 to 20-fold increase in viscosity. The polymer off However, Example 18 produced a two-fold increase after 3 days, but lost after 8 days quickly the viscosity and resulted in a 16% decrease in viscosity, indicating that the polymer backbone is degraded without additional Polymer is released and solubilized to compensate for this. The polymer in the bleach solution produced a cloudy Solution, indicating that polymer was available for thickening but not solubilized has been.

Claims (9)

Thickening bleach composition with controlled Release, comprising bleach, water and 0.1 to 50% by weight, based on the total weight of the thickening bleach composition, at least a crosslinked, carboxylated polymer consisting of 30 to 80% by weight at least one ethylenically unsaturated hydrophilic monomer, 20 to 70 wt .-% of at least one ethylenically unsaturated hydrophobic monomer and about 0.5 to about 10% by weight of a degradable crosslinking monomer selected from the group consisting of a crosslinking monomer which is at least two ethylenically unsaturated Has a crosslinking monomer that has at least one group ethylenically unsaturated group and at least one functional group that is capable of another functional group on a monomer to form a degradable Networking, and combinations thereof, has been made wherein the weight percentages are based on the total monomer weight, used for the preparation of the crosslinked carboxylated polymer is, are related. Thickening bleach composition with controlled Release, comprising bleach, water and 0.1 to 50% by weight, based on the total weight of the thickening bleach composition, at least a crosslinked carboxylated polymer consisting of 30 to 80% by weight at least one ethylenically unsaturated hydrophilic monomer, 20 to 70 wt .-% of at least one ethylenically unsaturated hydrophobic monomer and about 0.5 to about 10% by weight of a degradable crosslinking monomer selected from the group consisting of acrylic acid esters, methacrylic acid esters, maleic acid esters, crotonic Esters with allyl or methallyl alcohol, allyl ethers, vinyl ethers, Allyl sucrose ethers, thioamides, unsaturated epoxides, N-methylolacrylamide, Isocyanates and silanes, was prepared. Thickening bleach composition with controlled A release according to claim 2, wherein the degradable crosslinking monomer from the group consisting of glycidyl methacrylate, 2-isocyanatoethyl methacrylate, α, α-dimethylmeta-isopropenylbenzyl isocyanate, Vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, ethylene glycol dimethacrylate, Polyethylene glycol diacrylate, butanediol diacrylate, pentaerythritol tetraacrylate, Trimethylolpropane triacrylate, diallyl phthalate, diallyl maleate, allyl methacrylate, Vinyl crotonate, triallyl cyanurate, diallyl phosphate, ethanedithiol diacrylate and N, N'-methylenebisacrylamide selected is. Thickening bleach composition with controlled A release according to claim 1, wherein the crosslinked carboxylated polymer from 50 to 70% by weight of at least one hydrophilic monomer, 30 to 50% by weight of at least one hydrophobic monomer and about 1 to about 5 wt .-% of a degradable crosslinking monomer was prepared Thickening bleach composition with controlled A release according to claim 1, wherein the ethylenically unsaturated hydrophilic Monomer from the group consisting of acids, amides, ethers, alcohols, Aldehydes, ketones, esters and combinations thereof. The thickening bleach controlled release composition of claim 1, wherein the ethylenically unsaturated hydrophobic monomer is selected from the group consisting of C ₅ -C ₂₄ alkenyl, C ₅ -C ₂₄ alkenyloxy, and combinations thereof. Thickening bleach composition with controlled A release according to claim 1 which is at least one surfactant Medium, selected from the group consisting of anionic surfactants, cationic surfactants Agents, nonionic surfactants Agents, zwitterionic surfactants Agents and amphoteric surfactants Means, includes. A controlled release thickening bleach composition according to claim 1, further comprising at least one additive selected from the group consisting of dye transfer inhibitors, anti corrosive materials, antistatic agents, optical brighteners, perfumes, fragrances, dyes, fillers, electrolytes, buffers, chelants, fabric whiteners, brighteners, suds control agents, buffering agents, soil release agents, fabric softeners and combinations thereof. Thickening bleach composition with controlled A release according to claim 1, wherein the crosslinked carboxylated polymer in an amount of 1 to 10 wt .-%, based on the total weight the thickening bleach composition with controlled Release, is present.