Patent Grant
7935666
1. Technical Field
This invention relates to copolymers having amine functionality. More specifically, the present invention relates to homopolymers and copolymers having amine functionality, wherein the polymers contain a substantial degree of neutralization with an organic acid. The polymers are useful in providing color protection in laundry and textile applications.
2. Background Information
Fabrics and textiles can become soiled over time, requiring cleaning. Cleaning these fabrics and textiles removes dirt from the fibers; however, fibers can be dislodged from the woven and knit fabrics or textiles in the process, resulting in lint, fuzz, or pills that can remain on the surface of the material. Not only are fibers lost, the cleaning process can also remove at least some of the dyes, resulting in the fading of the fabric. Both losses are detrimental to the fabric and result in an undesirable appearance.
Detergents, therefore, are formulated with additives designed to associate with the fibers, and diminish the effect of wear, fiber loss, pilling and color-loss. An effective protective additive must (a) have the ability to associate with the surface of the fibers, and not be easily removed, and (b) not adversely effect detergency or cleaning properties of the detergent, i.e., not attract dirt and other soils back onto the fibers.
One method of associating the protective additive to the fiber is to make use of the anionic nature of the fiber. Additives containing cationic moieties are attracted to and associate with anionic fibers, thereby providing some protection to the fibers. Detergents containing linear polyamines are used in laundry detergent applications using this principal. The use of polyamines for this application is described in International Publication Nos. WO 99/14297, WO 00/49124, and U.S. Pat. No. 6,140,292.
International Publication No. WO 00/56849 discloses laundry detergent compositions having cationically charged polymers. The polymers are amine-containing homopolymers, copolymers, or quaternized derivatives thereof. This application maximizes the cationic component of the polymer, thereby increasing association between the polymer and the fibers. Anions are only disclosed in association with quaternized polymers. Unfortunately, cationic polymer additives also attract dirt. Therefore, dirt which has been removed from the laundry is attracted back to the cationic polymer and thus back to the clothes.
Another approach for associating a polymeric protective additive with fibers is to utilize the relative hydrophobic nature of the fibers compared to the aqueous environment of the wash liquor. Hydrophobic polymers associate with fibers and minimize exposure to the aqueous environment. On the other hand, polymers having a high hydrophilic character, such as many of the polyamines and poly amino acids described in the art, associate with the aqueous wash liquor, and do not deposit well onto the surface of the fibers. One way to overcome this disadvantage is to form a polymer having quaternized amines, such as is disclosed in International Publication No. WO 00/22075. These polymers have a high hydrophilic character, but are attracted to fibers due to the strong cationic character. The negative side of the high cationic character is the attraction for dirt and thus poor redeposition properties.
Polymers having a high degree of hydrophobicity are difficult to synthesize since they tend to be water insoluble and come out of solution when placed into an aqueous solution. The solubility of the polymer can be improved by reducing the level of hydrophobe; however, this also reduces the positive fiber deposition properties associated with the hydrophobe.
Polymers having a high degree of hydrophobicity are described in U.S. Publication No. 2003/00720950. The hydrophobically modified solution polymers can be used to provide color protection and anti-pilling properties to fabrics and textiles. The polymers contain at least 75 mole percent (mol %) of the hydrophobic monomer, and the hydrophobic amine monomer is neutralized to improve solubility.
Still, there is a need for a polymeric additive useful in protecting fibers during the cleaning process and having the proper balance between hydrophilic, hydrophobic, and cationic components, thereby providing excellent protective properties to fibers while minimizing the negative effect on redeposition properties associated with cationic character. While not being bound to any theory, it is believed that the hydrophobe serves to minimize the interaction of the amine functionality with surfactants typically found in a detergent. The copolymer should balance the water solubility (amine groups) and the water insolubility (hydrophobic groups) on the polymer molecule in order to optimize desired properties.
It has been found that amine functional copolymers that are at least partially neutralized and have greater than about 20 mol % of the amine moiety, balanced with a suitable level of nonionic and/or hydrophobic moieties, provide the advantage of color and wear protection to fibers with a minimum of negative effects on redeposition properties.
It has further been found that an amine functional (co)polymer having greater than 70 mol % of the amine moiety, wherein at least 75 mol % of the amine moiety has been neutralized with a suitable organic acid, provides the advantage of color and wear protection to fibers with a minimum of negative effects on redeposition properties.
Accordingly, the present invention is directed to a detergent composition having from about 3 to about 75 percent by weight of the total composition of at least one surfactant and from about 0.01 to about 5 percent by weight of the total composition of at least one copolymer. The copolymer is formed from about 70 to 100 mol %, based on the total mol % of the copolymer, of at least one amine-functional monomer, from 0 to about 30 mol %, based on the total mol % of the copolymer, of at least one hydrophobic ethylenically unsaturated monomer, from 0 to about 30 mol %, based on the total mol % of the copolymer, of an hydroxy functional ethylenically unsaturated monomer, and from 0 to about 10 mol %, based on the total mol % of the copolymer, of a diethylenically unsaturated monomer or polyfunctional mercaptan. The amine-functional monomer used in forming the copolymer is not a quaternized amine. The copolymer has been at least 75 mol % neutralized with an organic acid. In other embodiments, the copolymer can also be formed from additional monomers such as 0 to about 30 mol %, based on the total mol % of the copolymer, of an acid functional monomer, and 0 to about 10 mol %, based on the total mol % of the copolymer, of a hydroxy, alkyl or aromatic capped poly(alkoxylated) monomer.
The invention is also directed to a woven or knit natural fibrous material that is coated on at least one side with a copolymer formed from about 70 to 100 mol %, based on the total mol % of the copolymer, of at least one amine-functional monomer, from 0 to about 30 mol %, based on the total mol % of the copolymer, of at least one hydrophobic ethylenically unsaturated monomer, from 0 to about 30 mol %, based on the total mol % of the copolymer, of an hydroxy functional ethylenically unsaturated monomer, and from 0 to about 10 mol %, based on the total mol % of the copolymer, of a diethylenically unsaturated monomer or polyfunctional mercaptan. The amine-functional monomer used in forming the copolymer is not a quaternized amine. The copolymer can further be formed from additional monomers such as from 0 to about 30 mol %, based on the total mol % of the copolymer, of an acid functional monomer and from 0 to about 10 mol %, based on the total mol % of the copolymer, of a hydroxy, alkyl or aromatic capped poly(alkoxylated) monomer.
The present invention relates to a copolymer that is synthesized from at least one amine-functional monomer, and from at least one hydrophobic ethylenically unsaturated monomer.
Amine functional monomers useful in the invention include mono-, di-, tri-, and multi-amines. Examples of useful amine monomers include, but are not limited to N,N-dialkyl aminoalkyl (meth)acrylate, N,N-dialkyl aminoalkyl acrylate, dialkyl aminoalkyl (meth)acrylamide and N,N-dialkyl aminoalkyl acrylamide, where the alkyl groups are independently C1-18. Aromatic amine containing monomers such as vinyl pyridine may also be used. One skilled in the art will also be able to incorporate an amine functionality by reaction with a polymerizable anhydride (e.g., maleic anhydride), epoxide (e.g., glycidyl methacrylate), trans-esterification or condensation esterification or amidation. Furthermore, monomers such as vinyl formamide, vinyl acetamide, and the like which generate amine moieties on hydrolysis may also be used. In one embodiment the hydrophilic acid-neutralizable monomer is N,N-dimethyl aminoethyl methacrylate, N,N-dimethyl aminopropyl methacrylamide, or a mixture thereof. The amine does not include quaternary amines. It has been found that quaternary amines produce unsatisfactory redeposition properties. The copolymer is formed from about 70 to about 100 mol %, based on the total mol % of the copolymer, of the amine-functional monomer, which is neutralized to at least 75 mol % of the available amine with an organic acid.
The organic acid can be any weak acid containing a carbon atom. In one embodiment, the organic acids are carboxylic acids. In a further embodiment, the organic acids are polyfunctional acids. Examples of useful organic acids include but are not limited to; formic, acetic, propionic butyric, valeric, hexanoic, heptanoic, octanoic, nonanoic, decanoic, lauric, myristic, palmitic, stearic, oleic, linoleic, crotonic, maleic, fumaric, trifluoroacetic, glycolic, lactic, hydroxybutyric, malic, tartaric, gluconic, glyoxilic, pyruvic, benzoic, oxalic, citric, adipic, malonic, succinicglutaric, pimelic, suberic, azelaic, sebacic, polymaleic, polyacrylic.
The hydrophobic monomer can be any ethylenically unsaturated monomer known in the art, or a mixture thereof Examples of such monomers include, but are not limited to: (meth)acrylates, maleates, (meth)acrylamides, vinyl esters, itaconates, styrenics, unsaturated hydrocarbons and acrylonitrile, nitrogen functional monomers, vinyl esters, alcohol functional monomers, unsaturated hydrocarbons, and alkoxylated C8-C22 (meth)acrylates. Preferred hydrophobic monomers are vinyl monomers and acrylate monomers such as methyl methacrylate, ethyl acrylate, and butyl acrylate. The copolymer is formed from about 0 to about 30 mol % of the hydrophobic monomer.
In addition to the amine-functional monomer(s) and the hydrophobic monomer(s) the polymer of the invention may contain other monomeric units as known in the art, including, but not limited to, up to 30 mole percent based on the total mol % of the copolymer, of an hydroxy functional ethylenically unsaturated monomer, up to 10 mol %, based on the total mol % of the copolymer, of a diethylenically unsaturated monomer or a polyfunctional mercaptan, and/or up to 20 mol %, based on the total mol % of the copolymer, of a mono- or di-carboxylic acid monomer, up to 10 mole percent of an of a hydroxy, alkyl or aromatic capped poly(alkoxylated) monomer, or any combination thereof.
Small amounts of crosslinking monomer can be included in the polymer. If crosslinking monomers are used, preferably they form more flexible crosslinks, such as with polyethylene glycol diacrylate.
The copolymer is synthesized by solution polymerization techniques. The process involves polymerizing at least one amine-functional monomer and at least one hydrophobic ethylenically unsaturated monomer in a non-aqueous solvent, or non-aqueous/aqueous solvent mixture; forming an aqueous polymer dispersion; and adding an aqueous acid to at least partially neutralize the copolymer such that it becomes water soluble. The addition of the acid can occur either before, after, or during the formation of the aqueous polymer dispersion from the non-aqueous polymer solution.
The polymers formed from this type of process are generally random copolymers. However, other polymer architectures such as block, star etc may also be used. The special techniques used to synthesize these various types of polymer architecture are well known in the art.
The polymerization of the monomers in a non-aqueous solvent can be done by any means known in the art. The solvent should be miscible with water. Preferably the solvent is capable of forming an azeotrope with water. Examples of solvents useful in the present invention include, but are not limited to, alcohols such as methanol, ethanol, and isopropyl alcohol; glycol ethers; and acetone. If the solvent is a low boiling solvent, such as an alcohol or acetone, it can be stripped from the solution.
The final aqueous polymer composition can be formed by the combination of the conversion of the polymer solution to an aqueous solution and the addition of an acid. This results in a composition that can be either clear or hazy.
The amine copolymer can be combined with surfactants and other components known in the art. Useful surfactants are anionic, nonionic or a combination thereof.
Examples of suitable anionic surfactants include alkylaryl sulfonates, alkylaryl sulfonic acids, diphenyl sulfonates, ethoxylated fatty acids, olefin sulfonates, phosphate esters, propoxylated fatty acids, sulfates and sulfonates of fatty acids, sulfates and sulfonates of ethoxylated alkyl phenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfonates of dodecyl or trodecyl benzenes, and sulfosuccinamates.
Examples of suitable nonionic surfactants include alcohols, alkanolamides, ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated fatty esters and oils, fatty esters, glycerol esters, glycol esters, imidazolines, lanolin derivatives, monoglycerides, sorbitan esters, sucrose and glucose esters,
Ingredients such as surfactants can be used in combination with the copolymer in formulating detergent compositions. The detergent composition is preferably a laundry composition and can be in the form of granules, extrudates, flakes, tablets, liquids, gels, discrete doses or pastes.
The detergent composition can include about 3 to about 75 percent by weight of the total composition of surfactant(s), 0 to 55 percent by weight of the total composition builder(s), and about 15 to about 95 percent by weight of the total composition of a combination of optional ingredients, such as buffers, enzymes, softeners, antistatic agents, fluorescers, dyes, perfumes, water and fillers. The amine copolymer is used in amount of from about 0.01 to about 5.0 percent of the total composition. In another aspect, the copolymer is used in amount of from about 0.01 to about 2.5 percent. In even another aspect, the copolymer is used in amount of from about 0.1 to about 2 percent by weight of the detergent formulation.
Other optional components of the detergent formulations include, but are not limited to, ion exchangers, alkalis, anticorrosion materials, anti-redeposition materials, optical brighteners, fragrances, dyes, fillers, chelating agents, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, soil removal agents, soil release agents, fabric softening agent and opacifiers.
In a laundering process, the detergent composition is applied to a fibrous material in an aqueous medium. The fibrous material can be a woven or knit fabric composed of natural fibers, synthetic fibers, or a mixture thereof. In one embodiment, the fibrous material is formed from natural fibers such as cotton, wool or silk.
In a textile finishing process, the amine copolymer contacts the textile by padding or immersion process, an exhaustion process, or other processes known in art. The amine copolymer provides anti-pilling and color protection to the textile or fabric. Textiles such as carpet can be treated with the amine polymer, either as an initial or subsequent treatment.
The hydrophobically modified amine copolymer is also useful as an additive to hard surface cleaners where they improve cleaning and extend the time interval between cleaning, in autodish applications to minimize filming or spotting on glassware. Additionally, the polymers have good film forming properties making them useful for coating or encapsulating an active ingredient that may be released by dissolution in water or triggered by a change in pH.
The following examples are presented to further illustrate and explain the present invention and should not be taken as limiting in any regard. All percentages are based on mole and not weights.
To a 2 liter glass vessel equipped with; reflux condenser, stirrer, means of temperature control, 400 g water and 300 g propan-2-ol were charged then heated to a gentle reflux. A monomer mixture of dimethyl aminoethyl methacrylate (106.6 g) and methyl methacrylate (160 g) was fed into the reactor over an approximate timeframe of 3 hours. Sodium persulfate solution (8.7 g in 125 g of water) was fed concurrently with the monomer over a similar time period. When feeds were complete acetic acid solution (36.6 g in 150 g water) was fed into the reactor. A propan-2-ol azeotrope was then distilled from the reactor.
To a 2 liter glass vessel equipped with; reflux condenser, stirrer, means of temperature control, 300 g deionized water and 300 g propan-2-ol were charged then heated to a gentle reflux. A monomer mixture of dimethyl aminoethyl methacrylate (134.6 g) and ethyl acrylate (200 g) was fed into the reactor over an approximate timeframe of 3 hours. Sodium persulfate solution (3.4 g in 125 g of water) was fed concurrently with the monomer over a similar time period. When feeds were a propan-2-ol azeotrope was then distilled from the reactor, followed by neutralization with acetic acid (41.2 g).
To a 2 liter glass vessel equipped with; reflux condenser, stirrer, means of temperature control, 400 g water and 300 g propan-2-ol were charged then heated to a gentle reflux. A monomer mixture of dimethyl aminoethyl methacrylate (143.1 g) and methyl methacrylate (136.7 g) was fed into the reactor over an approximate timeframe of 3 hours. Sodium persulfate solution (8.7 g in 110 g of water) was fed concurrently with the monomer over a similar time period. When feeds were complete, hydrochloric acid solution (79.6 g of 37.6% active in 100 g water) was fed into the reactor. Residual monomers were scavenged over a 1 hour timeframe with sodium persulfate (1.5 g in 30 g of water). A propan-2-ol azeotrope was then distilled from the reactor with the aid of a defoaming agent (Foamblast 552 (0.16 g) available from Ross Chem. Inc.). Distillate was replaced w/w with water during distillation.
To a 2 liter glass vessel equipped with; reflux condenser, stirrer, means of temperature control, 400 g water and 300 g propan-2-ol were charged then heated to a gentle reflux. A monomer mixture of dimethyl aminoethyl methacrylate (177.7 g) and methyl methacrylate (114.3 g) was fed into the reactor over an approximate timeframe of 3 hours. Sodium persulfate solution (8.7 g in 110 g of water) was fed concurrently with the monomer over a similar time period. When feeds were complete, hydrochloric acid solution (90 g of 32% active in 100 g water) was fed into the reactor. Residual monomers were scavenged over a 1 hour timeframe with sodium persulfate (1.5 g in 30 g of water). A propan-2-ol azeotrope was then distilled from the reactor with the aid of a defoaming agent (Foamblast 552 (0.16 g) available from Ross Chem. Inc.). Distillate was replaced w/w with water during distillation.
To a 2 liter glass vessel equipped with; reflux condenser, stirrer, means of temperature control, 400 g water and 300 g propan-2-ol were charged then heated to a gentle reflux. A monomer mixture of dimethyl aminoethyl methacrylate (106.6 g) and methyl methacrylate (113.9 g) and hydroxypropyl methacrylate (65.6 g) was fed into the reactor over an approximate timeframe of 3 hours. Sodium persulfate solution (8.7 g in 110 g of water) was fed concurrently with the monomer over a similar time period. When feeds were complete, hydrochloric acid solution (62.7 g of 37.6% active in 100 g water) was fed into the reactor. Residual monomers were scavenged over a 1 hour timeframe with sodium persulfate (1.5 g in 30 g of water). A propan-2-ol azeotrope was then distilled from the reactor with the aid of a defoaming agent (Foamblast 552 (0.16 g) available from Ross Chem. Inc.). Distillate was replaced w/w with water during distillation.
To a 2 liter glass vessel equipped with; reflux condenser, stirrer, means of temperature control, 400 g water and 300 g propan-2-ol were charged then heated to a gentle reflux. A monomer mixture of dimethyl aminoethyl methacrylate (106.6 g) and methyl methacrylate (113.9 g) and hydroxybutyl methacrylate (72.0 g) was fed into the reactor over an approximate timeframe of 3 hours. Sodium persulfate solution (8.7 g in 110 g of water) was fed concurrently with the monomer over a similar time period. When feeds were complete, hydrochloric acid solution (62.7 g of 37.6% active in 100 g water) was fed into the reactor. Residual monomers were scavenged over a 1 hour timeframe with sodium persulfate (1.5 g in 30 g of water). A propan-2-ol azeotrope was then distilled from the reactor with the aid of a defoaming agent (Foamblast 552 (0.16 g) available from Ross Chem Inc.). Distillate was replaced w/w with water during distillation.
A color protection evaluation was performed using lab-produced liquid built detergent. A base-line sample was run with the complete detergent and no polymer, then a control, which consisted of the complete detergent and the polymer of Example 4. The test was then designed to omit one component from the detergent for each of the runs, but included the same polymer in each. Swatches of seven different colors were washed in each of the detergent combinations, and the Delta E (difference in color after washing) was calculated after five complete wash/dry cycles.
Liquid Built Detergent (LBD) Formulation:
Test Conditions—
The anti-pilling tests were conducted as follows. The test was conducted over 5 or 10 full cycles using 118 g/load Xtra liquid detergent and 1% active polymer on detergent. The wash temperature was 93° F., with a 10-minute wash and a cold rinse. The wash water was Chattanooga City water, which typically has a hardness of 70 ppm. 3 black knit swatches (Cotton Interlock knit TIC 460 from Textile innovators) and 3 white swatches (Bleached Cotton Interlock knit TIC 460 from Textile innovators) were attached to one pillowcase and 10 ballast pillowcases were used as ballast. The white knit swatches were used to visually evaluate pilling, and the black knit swatches were used to evaluate color protection using a spectrophotometer.
The copolymer of Example 1 (dimethyl aminoethyl methacrylate (DMAEMA)-co-methyl methacrylate (MMA) (70 mol %)) was found to have excellent anti-pilling performance. Therefore, several evaluations were run on this polymer to determine if it would adversely affect laundry performance. Each evaluation is described below and followed by the results.
The polymer did not significantly interfere with optical brightener deposition.
Some small improvement in stain release was realized with the addition of the polymer.
The data in the Table indicates that the Example 1 copolymer has color protection properties in addition to anti-pilling properties. In addition, it can be used as a control release agent that is insoluble in the wash cycle but soluble in the rinse, thus delivering actives in the rinse.
The polymers tested are listed in the Table below.
The data in the Tables indicate that the homopolymer of DMDAAC and DMAEMA have very poor anti-redep performance. However, a hydrophobically modified amine polymer does not adversely affect anti-redep performance.
Acid Cleaner
Alkaline Cleaner
Polymers from Examples 2, 3 and 6 were cast onto a polyethylene surface and left to dry at room temperature.
The above films prepared from the polymers of Examples 2, 3 and 6 are soluble in water.
The polymer of Example 1 was diluted to a 1% solution. The pH was adjusted with 2% NaOH solution.
The polymer of Example 3 was diluted to a 1% solution. The pH was adjusted with 2% NaOH solution.
The polymer of example 6 was diluted to a 1% solution. The pH was adjusted with 2% NaOH solution.
Water (200 g) and citric acid (96 g, 0.5 mol) were added to a 1 liter glass reactor equipped with means of stirring, temperature control and reflux condenser. The reactor contents were heated to 90° C. Dimethylaminoethyl methacrylate (DMAEMA, 78.8 g, 0.5 mol) was fed into the reactor over a period of 2.5 hours. Separately and concurrently with the DMAEMA, an aqueous solution of sodium persulfate (3 g) was fed into the reactor over a period of 3 hours. The polymerization was scavenged with sodium persulfate (1 g) aqueous feed for one additional hour.
Color Protection Assessment Test Conditions—
The results demonstrate that the polymer of Example 18 ((poly)DMAEMA) has excellent color protection properties.
Anti Redeposition Test Conditions—
The above results illustrated that the fully neutralized polyamine has little effect on soil redeposition.
Soil Anti-Redepositon Test Conditions
The above results illustrates that the partially neutralized polymer of Example 18 ((poly)DMAEMA) negatively impacts cleaning.
Although the present invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example only, and is not to be taken as a limitation. The spirit and scope of the present invention are to be limited only by the terms of any claims presented hereafter.
The present application is a continuation-in-part of U.S. Pat. No. 6,924,259, issued Aug. 2, 2005.
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| Number | Date | Country |
|---|---|---|
| 43 23 638 | Jan 1995 | DE |
| 1 199 326 | Apr 2002 | EP |
| WO 9502674 | Jan 1995 | WO |
| WO 9914297 | Mar 1999 | WO |
| WO 0022075 | Apr 2000 | WO |
| WO 0049124 | Aug 2000 | WO |
| WO 0056849 | Sep 2000 | WO |
| WO 03011969 | Feb 2003 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20050148489 A1 | Jul 2005 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10124358 | Apr 2002 | US |
| Child | 11061602 | US |
