Patent Application
20170255725
The present invention relates to substrates comprising malodor reduction compositions and methods of making and using such substrates.
Unscented or scented products are desired by consumers as they may be considered more natural and discreet than scented products. Manufacturers of unscented or scented products for controlling malodors rely on malodor reduction ingredients or other technologies (e.g. filters) to reduce malodors. However, effectively controlling malodors, for example, amine-based malodors (e.g. fish and urine), thiol and sulfide-based malodors (e.g. garlic and onion), C2-C12 carboxylic acid based malodors (e.g. body and pet odor), indole based malodors (e.g. fecal and bad breath), short chain fatty aldehyde based malodors (e.g. grease) and geosmin based malodors (e.g. mold/mildew) may be difficult, and the time required for a product to noticeably reduce malodors may create consumer doubt as to the product's efficacy on malodors. Often times, manufacturers incorporate scented perfumes to help mask these difficult malodors.
Unfortunately, malodor control technologies typically cover up the malodor with a stronger scent and thus interfere with the scent of the perfumed or unperfumed situs that is treated with the malodor control technology. Thus, limited nature of the current malodor control technologies is extremely constraining. Thus what is needed is a broader palette of malodor control technologies so the perfume community can deliver the desired level of character in a greater number of situations/applications. Surprisingly, Applicants recognized that in addition to blocking a malodor's access to a sensory cell, in order to achieve the desired goal, a malodor control technology must leave such sensor cell open to other molecules, for example scent molecules. As a result, such malodor reduction compositions do not unduely interfere with the scent of the perfumed or unperfumed substrates comprising such malodor reduction compositions and the perfumed or unperfumed situs that is treated with such substrates.
The present invention relates to substrates comprising malodor reduction compositions and methods of making and using such substrates. Such malodor reduction compositions do not unduely interfere with the scent of the perfumed or unperfumed substrates comprising such malodor reduction compositions and the perfumed or unperfumed situs that is treated with such substrates.
As used herein “MORV” is the calculated malodor reduction value for a subject material. A material's MORV indicates such material's ability to decrease or even eliminate the perception of one or more malodors. For purposes of the present application, a material's MORV is calculated in accordance with method found in the test methods section of the present application.
As used herein, the term “perfume” does not include malodor reduction materials. Thus, the perfume portion of a composition does not include, when determining the perfume's composition, any malodor reduction materials found in the composition as such malodor reduction materials are described herein. In short, if a material has a malodor reduction value “MORV” that is within the range of the MORV recited in the subject claim, such material is a malodor reduction material for purposes of such claim.
As used herein, “malodor” refers to compounds generally offensive or unpleasant to most people, such as the complex odors associated with bowel movements.
As used herein, “odor blocking” refers to the ability of a compound to dull the human sense of smell.
As used herein, “odor masking” refers to the ability of a compound with a non-offensive or pleasant smell that is dosed such that it limits the ability to sense a malodorous compound. Odor-masking may involve the selection of compounds which coordinate with an anticipated malodor to change the perception of the overall scent provided by the combination of odorous compounds.
As used herein, the terms “a” and “an” mean “at least one”.
As used herein, the terms “include”, “includes” and “including” are meant to be non-limiting.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
A non-limiting set of suitable malodor reduction materials are provided in the tables below. For ease of use, each material in Tables 1-3 is assigned a numerical identifier which is found in the column for each table that is designated Number. Table 4 is a subset of Table 1, Table 5 is a subset of Table 2 and Table 6 is a subset of Table 3 and there for Tables 4, 5 and 6 each use the same numerical identifier as found, respectively, in Tables 1-3.
The materials in Tables 1-6 can be supplied by one or more of the following:
Firmenich Inc. of Plainsboro N.J. USA; International Flavor and Fragrance Inc. New York, N.Y. USA; Takasago Corp. Teterboro, N.J. USA; Symrise Inc. Teterboro, N.J. USA; Sigma-Aldrich/SAFC Inc. Carlsbad, Calif. USA; and Bedoukian Research Inc. Danbury, Conn. USA.
Actual MORV values for each material listed in Tables 1-6 above are as follows:
An article comprising
In one aspect of said article, said malodor reduction materials have a Fragrance Fidelity Index of from about less than 3, more preferable less than about 2.5 even more preferably less than about 2 and still more preferably less than about 1 and most preferably 0 or a Fragrance Fidelity Index average of 3 to about 0.001.
In one aspect of said article, said article comprises a perfume, said article having a weight ratio of parts of malodor reduction composition to parts of perfume of from about 1:20,000 to about 3000:1, preferably from about 1:10,000 to about 1,000:1, more preferably 5,000:1 to about 500:1 and most preferably from about 1:15 to about 1:1.
In one aspect of said article, said article comprises one or more malodor reduction materials having a log P greater than 3, preferably greater than 3 but less than 8, preferably said one or more malodor reduction materials are selected from the group consisting of Table 1 materials 1; 2; 3; 7; 9; 10; 11; 13; 14; 18; 21; 22; 23; 25; 28; 29; 30; 31; 32; 33; 35; 36; 38; 39; 47; 48; 49; 50; 52; 57; 62; 63; 64; 67; 68; 69; 71; 74; 75; 76; 77; 78; 79; 80; 83; 85; 91; 92; 93; 100; 101; 102; 103; 104; 105; 109; 114; 119; 120; 122; 123; 128; 134; 135; 137; 140; 142; 145; 148; 149; 152; 153; 158; 159; 161; 162; 174; 175; 176; 177; 178; 182; 183; 184; 185; 186; 189; 192; 195; 196; 197; 206; 208; 209; 210; 211; 212; 215; 221; 227; 228; 229; 230; 231; 233; 234; 238; 242; 243; 244; 246; 252; 253; 260; 261; 263; 267; 269; 271; 274; 276; 277; 280; 285; 289; 290; 292; 293; 294; 295; 296; 300; 301; 303; 307; 316; 317; 318; 322; 324; 325; 328; 329; 330; 331; 333; 334; 335; 336; 338; 339; 342; 343; 344; 349; 352; 356; 358; 359; 360; 361; 362; 363; 364; 368; 369; 370; 371; 372; 378; 381; 385; 386; 388; 390; 391; 397; 398; 413; 414; 416; 418; 421; 424; 426; 428; 429; 432; 441; 444; 449; 453; 457; 459; 461; 462; 463; 465; 466; 467; 468; 470; 471; 473; 475; 478; 479; 480; 482; 484; 486; 487; 488; 497; 498; 501; 502; 503; 505; 519; 520; 521; 524; 529; 532; 534; 537; 541; 544; 548; 550; 552; 558; 559; 560; 561; 562; 563; 565; 566; 567; 568; 569; 570; 571; 572; 573; 574; 577; 578; 582; 584; 589; 591; 592; 594; 599; 600; 601; 603; 604; 606; 607; 608; 609; 610; 611; 613; 614; 615; 616; 618; 620; 621; 624; 625; 626; 628; 631; 632; 633; 635; 644; 650; 653; 659; 660; 661; 663; 671; 673; 674; 675; 676; 677; 678; 679; 680; 681; 684; 686; 691; 692; 693; 694; 696; 697; 698; 700; 702; 704; 706; 707; 708; 709; 710; 711; 712; 713; 714; 715; 716; 717; 718; 719; 720; 721; 722; 723; 724; 725; 726; 727; 731; 741; 746; 750; 752; 754; 757; 758; 763; 766; 769; 770; 771; 774; 775; 776; 778; 781; 782; 788; 791; 800; 802; 804; 806; 814; 821; 826; 827; 828; 831; 837; 839; 840; 849; 850; 852; 856; 866; 868; 869; 870; 871; 872; 873; 876; 877; 878; 879; 881; 884; 885; 886; 890; 892; 893; 894; 905; 908; 912; 913; 914; 916; 919; 920; 922; 925; 926; 927; 930; 933; 939; 941; 942; 943; 945; 947; 948; 950; 951; 953; 954; 959; 965; 967; 973; 978; 985; 988; 998; 1000; 1003; 1006; 1007; 1008; 1009; 1010; 1016; 1022; 1023; 1024; 1025; 1028; 1029; 1031; 1032; 1033; 1035; 1038; 1045; 1046; 1047; 1053; 1057; 1060; 1062; 1063; 1065; 1067; 1070; 1073; 1075; 1077; 1078; 1082; 1089; 1090; 1093; 1095; 1097; 1099; 1102; 1104; 1105; 1107; 1116; 1120; 1121; 1126; 1129; 1131; 1135; 1136; 1137; 1138; 1140; 1142; 1143; 1144; 1145; 1147; 1148; 1149; Table 2 materials 2; 23; 185; 227; 230; 246; 248; 343; 359; 565; 631; 659; 674; 678; 679; 715; 758; 1028; 1097; Table 3 materials 1; 9; 12; 13; 19; 20; 21; 24; 25; 27; 32; 38; 54; 55; 59; 64; 68; 71; 72; 79; 81; 83; 85; 100; 105; 109; 111; 114; 119; 133; 134; 135; 137; 140; 142; 147; 148; 150; 151; 152; 153; 154; 157; 159; 162; 178; 181; 189; 191; 192; 195; 197; 204; 211; 228; 231; 233; 234; 237; 238; 242; 246; 252; 264; 270; 273; 275; 277; 283; 285; 289; 290; 292; 293; 295; 300; 301; 302; 306; 308; 310; 312; 319; 322; 325; 331; 333; 334; 336; 338; 339; 344; 346; 354; 355; 356; 358; 361; 362; 363; 370; 371; 372; 378; 381; 385; 387; 388; 390; 412; 413; 418; 420; 428; 429; 432; 437; 438; 444; 447; 448; 454; 455; 457; 461; 465; 467; 472; 477; 478; 479; 480; 481; 482; 495; 496; 497; 502; 503; 504; 509; 510; 512; 515; 517; 518; 522; 525; 529; 535; 536; 537; 540; 541; 544; 550; 557; 558; 559; 560; 561; 568; 571; 572; 575; 589; 592; 594; 599; 600; 602; 604; 609; 619; 620; 625; 626; 633; 641; 644; 645; 650; 653; 662; 667; 672; 673; 675; 676; 681; 686; 687; 693; 697; 698; 700; 703; 704; 706; 707; 716; 717; 718; 722; 725; 744; 745; 746; 757; 769; 771; 779; 782; 799; 806; 819; 820; 827; 828; 836; 838; 839; 847; 850; 875; 878; 879; 880; 881; 888; 889; 890; 891; 893; 899; 900; 901; 903; 909; 912; 914; 920; 922; 930; 939; 940; 941; 945; 947; 948; 953; 954; 958; 959; 960; 965; 967; 971; 986; 987; 994; 995; 998; 1000; 1001; 1003; 1005; 1008; 1009; 1010; 1011; 1017; 1018; 1023; 1031; 1032; 1046; 1047; 1051; 1052; 1053; 1054; 1055; 1057; 1058; 1061; 1062; 1063; 1074; 1075; 1076; 1082; 1088; 1093; 1095; 1099; 1102; 1104; 1105; 1115; 1116; 1120; 1127; 1128; 1134; 1135; 1141; 1147; 1148, 1149, and mixtures thereof; preferably said malodor reduction materials are selected from the group consisting of Table 1 materials 1; 2; 3; 7; 9; 10; 11; 13; 14; 18; 21; 22; 23; 25; 28; 29; 30; 31; 32; 33; 35; 36; 38; 39; 47; 48; 49; 50; 52; 57; 62; 63; 64; 67; 68; 69; 71; 74; 75; 76; 77; 78; 79; 80; 83; 85; 91; 92; 93; 100; 101; 102; 103; 104; 105; 109; 114; 119; 120; 122; 123; 128; 134; 135; 137; 140; 142; 145; 148; 149; 152; 153; 158; 159; 161; 162; 174; 175; 176; 177; 178; 182; 183; 184; 185; 186; 189; 192; 195; 196; 197; 206; 208; 209; 210; 211; 212; 215; 221; 227; 228; 229; 230; 231; 233; 234; 238; 242; 243; 244; 246; 252; 253; 260; 261; 263; 267; 269; 271; 274; 276; 277; 280; 285; 289; 290; 292; 293; 294; 295; 296; 300; 301; 303; 307; 316; 317; 318; 322; 324; 325; 328; 329; 330; 331; 333; 334; 335; 336; 338; 339; 342; 343; 344; 349; 352; 356; 358; 359; 360; 361; 362; 363; 364; 368; 369; 370; 371; 372; 378; 381; 385; 386; 388; 390; 391; 397; 398; 413; 414; 416; 418; 421; 424; 426; 428; 429; 432; 441; 444; 449; 453; 457; 459; 461; 462; 463; 465; 466; 467; 468; 470; 471; 473; 475; 478; 479; 480; 482; 484; 486; 487; 488; 497; 498; 501; 502; 503; 505; 519; 520; 521; 524; 529; 532; 534; 537; 541; 544; 548; 550; 552; 558; 559; 560; 561; 562; 563; 565; 566; 567; 568; 569; 570; 571; 572; 573; 574; 577; 578; 582; 584; 589; 591; 592; 594; 599; 600; 601; 603; 604; 606; 607; 608; 609; 610; 611; 613; 614; 615; 616; 618; 620; 621; 624; 625; 626; 628; 631; 632; 633; 635; 644; 650; 653; 659; 660; 661; 663; 671; 673; 674; 675; 676; 677; 678; 679; 680; 681; 684; 686; 691; 692; 693; 694; 696; 697; 698; 700; 702; 704; 706; 707; 708; 709; 710; 711; 712; 713; 714; 715; 716; 717; 718; 719; 720; 721; 722; 723; 724; 725; 726; 727; 731; 741; 746; 750; 752; 754; 757; 758; 763; 766; 769; 770; 771; 774; 775; 776; 778; 781; 782; 788; 791; 800; 802; 804; 806; 814; 821; 826; 827; 828; 831; 837; 839; 840; 849; 850; 852; 856; 866; 868; 869; 870; 871; 872; 873; 876; 877; 878; 879; 881; 884; 885; 886; 890; 892; 893; 894; 905; 908; 912; 913; 914; 916; 919; 920; 922; 925; 926; 927; 930; 933; 939; 941; 942; 943; 945; 947; 948; 950; 951; 953; 954; 959; 965; 967; 973; 978; 985; 988; 998; 1000; 1003; 1006; 1007; 1008; 1009; 1010; 1016; 1022; 1023; 1024; 1025; 1028; 1029; 1031; 1032; 1033; 1035; 1038; 1045; 1046; 1047; 1053; 1057; 1060; 1062; 1063; 1065; 1067; 1070; 1073; 1075; 1077; 1078; 1082; 1089; 1090; 1093; 1095; 1097; 1099; 1102; 1104; 1105; 1107; 1116; 1120; 1121; 1126; 1129; 1131; 1135; 1136; 1137; 1138; 1140; 1142; 1143; 1144; 1145; 1147; 1148; 1149; Table 2 materials 2; 23; 185; 227; 230; 246; 248; 343; 359; 565; 631; 659; 674; 678; 679; 715; 758; 1028; 1097 and mixtures thereof; more preferably said malodor reduction materials are selected from the group consisting of Table 4 materials 7; 14; 39; 48; 183; 206; 212; 215; 229; 260; 261; 329; 335; 360; 441; 484; 487; 488; 501; 566; 567; 569; 570; 573; 574; 603; 616; 621; 624; 632; 663; 680; 684; 694; 696; 708; 712; 714; 726; 750; 775; 776; 788; 804; 872; 919; 927; 933; 978; 1007; 1022; 1024; 1029; 1035; 1038; 1060; 1089; 1107; 1129; 1131; 1136; 1137; 1140; 1142; 1143; 1144; 1145; 1148, 1149 Table 5 material 248 and mixtures thereof, most preferably said material is selected from the group consisting of Table 4 materials 261; 680; 788; 1129, 1148, 1149 and mixtures thereof. All of the aforementioned materials have a log P that is equal to or greater than 3, thus they deposit through the wash especially well. The more preferred and most preferred of the aforementioned material are particularly preferred as they are effective at counteracting all of the key malodors.
In one aspect of said article, said malodor reduction materials are not selected from the group consisting of Table 1-3 malodor reduction materials 302; 288; 50; 157; 1017; 888; 64; 1054; 832; 375; 390; 745; 504; 505; 140; 1012; 498; 362; 103; 356; 1074; 908; 1127; 475; 918; 687; 611; 317; 9; 141; 550; 602; 913; 1005; 521; 10; 215; 370; 335; 378; 1121; 360; 565; 1136; 1129; 655; 369; 1065; 914; 757; 601; 478; 889; 891; 358; 973; 162; 554; 522; 312; 125; 26; 418; 92; 586; 1026; 218; 31; 828; 871; 829; 1066; 287; 269; 769; 701; 1118; 70; 946; 142; 109; 108 or mixtures thereof.
In one aspect of said article, said article having a weight ratio of fabric softener active to dry substrate ranging from about 10:1 to about 0.5:1, preferably from about 5:1 to about 1:1, preferably said fabric softener active is selected from the group consisting of a quaternary ammonium compound, a silicone polymer, a polysaccharide, a clay, an amine, a fatty ester, a dispersible polyolefin, a polymer latex and mixtures thereof.
In one aspect of said article, said article comprises a quaternary ammonium compound selected from the group consisting of bis-(2-hydroxypropyl)-dimethylammonium methylsulphate fatty acid ester, 1,2-di(acyloxy)-3-trimethylammoniopropane chloride, N, N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(stearoyl-oxy-ethyl)N-(2 hydroxyethyl)N-methyl ammonium methylsulfate, 1,2 di (stearoyl-oxy) 3 trimethyl ammoniumpropane chloride, dicanoladimethylammonium chloride, di(hard)tallowdimethylammonium chloride dicanoladimethyl ammonium methylsulfate, 1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium methylsulfate, 1-tallowylamidoethyl-2-tallowylimidazoline, Dipalmethyl Hydroxyethylammoinum Methosulfate and mixtures thereof.
In one aspect of said article, said article comprises a fabric softening active having an Iodine Value of between 0-140, preferably 5-100, more preferably 10-80, even more preferably, 15-70, most preferably 18-25.
In one aspect of said article, said article comprises an adjunct ingredient selected from the group consisting of surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, hueing dyes, perfumes, perfume delivery systems, structure elasticizing agents, carriers, structurants, hydrotropes, processing aids, solvents, pigments and mixtures thereof.
A method of controlling malodors comprising: contacting a situs comprising a malodor or that will develop a malodor with an one or more of the articles Applicants' disclose herein, is disclosed.
In one aspect of said method, said situs comprises a fabric and said contacting step comprises contacting said fabric with a sufficient amount of Applicants' article containing Malodor reducing composition to provide said fabric with a level of malodor reduction material at least 0.0025 mg of malodor reduction material/kg of fabric, preferably from about 0.00025 mg of malodor reduction material/kg of fabric to about 25 mg of malodor reduction material/kg of fabric, more preferably from about 0.025 mg of malodor reduction material/kg of fabric to about 20 mg of malodor reduction material/kg of fabric, most preferably from about 0.25 of malodor reduction material/kg of fabric to about 10 mg of malodor reduction material/kg of fabric of said sum of malodor reduction materials.
The article of the present invention can comprise at least one fabric conditioning compound. Typical levels of said fabric conditioning compounds within the conditioning compositions are from 1% to 99% by weight of the compositions. However, compositions of the present invention can also contain from about 1% to about 80%, preferably from about 20% to about 70%, more preferably from about 25% to about 60% of fabric conditioning component.
The fabric conditioning compound, or compounds, can be selected from cationic, nonionic, amphoteric and/or anionic fabric conditioning compounds. Cationic and/or nonionic conditioning compounds are preferred as they provide effective fabric softening and/or anti-static benefits and/or care benefits when applied to fabrics in the dryer. These compounds also aid in the delivery of odor/freshening ingredients and benefits when transferred to fabrics in the dryer.
The typical cationic fabric conditioning compounds include the quaternary-ammonium fabric conditioning actives, the most commonly used having been di(long alkyl chain)dimethylammonium (C1-C4 alkyl) sulfate or chloride, preferably the methyl sulfate. Quaternary ammonium fabric conditioning compounds include the following:
dipalmityldimethylammonium methyl sulfate
distearyldimethylammonium methyl sulfate;
dioleyldimethylammonium methyl sulfate;
di(tallowoyl)dimethylammonium methyl sulfate (DTDMAMS);
di(hydrogenated tallowoyl)dimethylammonium methyl sulfate;
di(C12-16 alkyl)dimethylammonium methyl sulfate;
palmoyltrimethylammonium methyl sulfate
stearoyltrimethylammonium methyl sulfate
oleoyltrimethylammonium methyl sulfate
tallowoyltrimethylammonium methyl sulfate
(hydrogenated tallowoyl)trimethylammonium methyl sulfate;
(C12-16 alkyl)trimethylammonium methyl sulfate
di(hydrogenated tallowoyl)dimethyiammonium chloride (DTDMAC);
stearylbenzyldimethylammonium methyl sulfate;
ditallowalkylimidazolinium methyl sulfate;
The currently preferred compounds are more environmentally-friendly materials, being rapidly biodegradable quaternary ammonium compounds that are alternatives to the traditionally used di(iong alkyl chain)dimethylarnmoni urn methyl sulfate. Such quaternary ammonium compounds can contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups.
A preferred fabric conditioning compound is an ester quaternary ammonium compound (EQA), their ester amine precursors, and mixtures thereof. By “amine precursors thereof” is meant the secondary or tertiary amines corresponding to the above quaternary ammonium compounds.
The preferred compounds can be considered to be diester quaternary ammonium salts (DEQA). At least about 25% of the DEQA is in the diester form, and from 0% to about 40%, preferably less than about 30%, more preferably less than about 20%, can be EQA monoester (As used herein, when the diester is specified, it will include the monoester that is normally present. For the optimal antistatic benefit the percentage of monoester should be as low as possible, preferably less than about 2.5%. The level of monoester present can be controlled in the manufacturing of the EQA.
EQA compounds prepared with fully saturated acyl groups are excellent softeners. However, it has now been discovered that compounds prepared with at least partially unsaturated acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met. Variables that must be adjusted to obtain the benefits of using unsaturated acyl groups include the Iodine Value of the fatty acids, the odor of fatty acid starting material, and/or the EQA. Any reference to Iodine Value values hereinafter refers to Iodine Value of fatty acyl groups and not to the resulting EQA compound.
Some highly desirable, readily available sources of fatty acids such as tallow, possess odors that remain with the compound EQA despite the chemical and mechanical processing steps which convert the raw tallow to finished EQA. Such sources must be deodorized, e.g., by absorption, distillation (including stripping such as steam stripping), etc., as is well known in the art. In addition, care must be taken to minimize contact of the resulting fatty acyl groups to oxygen and/or bacteria by adding antioxidants, antibacterial agents, etc.
Generally, hydrogenation of fatty acids to reduce polyunsaturation and to lower Iodine Value to insure good color and odor stability leads to a high degree of trans configuration in the molecule. Therefore, diester compounds derived from fatty acyl groups having low Iodine Value values can be made by mixing fully hydrogenated fatty acid with touch hydrogenated fatty acid at a ratio which provides an Iodine Value of from about 3 to about 60. The polyunsaturation content of the touch hardened fatty acid should be less than about 5%, preferably less than about 1%. During touch hardening the cis/trans isomer weight ratios are controlled by methods known in the art such as by optimal mixing, using specific catalysts, providing high availability, etc. It has also been found that for good chemical stability of the diester quaternary compound in molten storage, water levels in the raw material must be minimized to preferably less than about 8% and more preferably less than about 5%. Storage temperatures should be kept as low as possible and still maintain a fluid material, ideally in the range of from about 45.degree. C. to about 70.degree. C. The optimum storage temperature for stability and fluidity depends on the specific Iodine Value of the fatty acid used to make the diester quaternary and the level/type of solvent selected. Also, exposure to oxygen should be minimized to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal transportation/storage/handling of the material in manufacturing operations. A specific example of a EQA compound suitable for use in the fabric softening compositions herein is: 1,2-bis(tallowyl oxy)-3-trimethyl ammoniopropane methylsulfate (DTTMAPMS).
Other examples of suitable EQA compounds are obtained by, e.g., replacing “tallowyl” in the above compounds with, for example, cocoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing “methyl” in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals; and/or replacing “methylsulfate” in the above compounds with chloride, ethylsulfate, bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is preferred. Another example of a suitable EQA compound is: N-2-hydroxyethyl ammonium methylsulfate. A preferred compound is N-methyl, N,N-di-(2-oleyloxyethyl)N-2-hydroxyethyl ammonium methylsulfate.
Another example of a suitable compound is methyl bis (oleyl amidoethyl) 2-hydroxyethyl ammonium methyl sulfate.
The compounds herein can be prepared by standard esterification and quaternization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180, which is incorporated herein by reference.
Specific examples of EQA compounds include:
di(tallowoyloxyethyl)dimethylammonium methyl sulfate;
(tallowoyl)hydroxyethyldimethylammonium methyl sulfate;
di(tallowoylhydroxyethyl)methylammonium methyl sulfate;
tallowoyl(dihydroxyethyl)methylammonium methyl sulfate;
tri(tallowoylhydroxyethyl)ammonium methyl sulfate
(2-tallowylamidoethyl)-2-tallowylimidazolinium methyl sulfate; and
N-(tallowoyloxyethyl)-N-(tallowyl)-N,N-dimethyl-ammonium methyl sulfate;
methyl bis (oleyl amidoethyl) 2-hydroxyethyl ammonium methyl sulfate;
1,2-bis(tallowoyloxyethyl)-3,3,3-trimethyl ammoniopropane methylsulfate (DTTMAPMS); and
mixtures of any of the above materials.
Particularly preferred is N,N-di(tallowoyloxyethyl)-N,N-dimethyl ammonium methyl sulfate, where the tallow chains are fully hydrogenated or partially unsaturated.
Other examples of suitable compounds can be obtained by, replacing “tallowoyl” in the above compounds with, for example, cocoyl, lauroyl, oleoyl, stearoyl, palmitoyl, or the like, the fatty acyl chains being either fully saturated, or preferably at least partly unsaturated; The fatty acyl chains maybe mixed from natural or purified sources or blended from one or more sources; replacing “methyl” in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals; and/or replacing “methylsulfate” in the above compounds with chloride, ethylsulfate, bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is preferred.
The level of unsaturation of the acyl chain mixture can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100.
Another fabric conditioning active useful in the articles of the present invention is a carboxylic acid salt of a tertiary amine and/or ester amine said materials have a thermal softening point of from about 35.degree. C. to about 100.degree. C.
This component can provide superior odor and/or improved fabric softening performance, compared to similar articles which utilize primary amine or ammonium compounds as the sole fabric conditioning agent. Particularly preferred tertiary amines for static control performance are those containing unsaturation; e.g., oleyldimethylamine and/or soft tallowdimethylamine Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form the tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallowdimethylamine, coconutdimethylamine, dilaurylmethyl amine, distearylmethylamine, ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3-hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethylmethylamine, and
Examples of specific carboxylic acids as a starting material are: formic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid, benzoic acid, 4-hydroxy benzoic acid, 3-chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-chloroethyl)benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4-hydroxyphenyl)acetic acid, and phthalic acid. Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and mixtures thereof. The amine salt can be formed by a simple addition reaction, well known in the art and disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 1980, which is incorporated herein by reference. Excessive levels of free amines may result in odor problems, and generally free amines provide poorer softening performance than the amine salts. The amine and the acid, respectively, used to form the amine salt will often be of mixed chain lengths rather than single chain lengths, since these materials are normally derived from natural fats and oils, or synthetic processed which produce a mixture of chain lengths. Also, it is often desirable to utilize mixtures of different chain lengths in order to modify the physical or performance characteristics of the softening composition. Specific preferred amine salts for use in the present invention are oleyldimethylamine stearate, stearyldimethylamine stearate, stearyldimethylamine myristate, stearyldimethylamine oleate, stearyldimethylamine palmitate, distearylmethylamine palmitate, distearylmethylamine laurate, and mixtures thereof. A particularly preferred mixture is oleyldimethylamine stearate and distearylmethylamine myristate, in a ratio of 1:10 to 10:1, preferably about 1:1.
A softening active that can also be employed in the present invention is a nonionic fabric softener material. Typically, such nonionic fabric softener materials have an HLB of from about 2 to about 9, and more typically from about 3 to about 7. In general, the materials selected should be relatively crystalline and higher melting, (e.g., >25.degree. C.). The level of optional nonionic softener in the solid composition is typically from about 0.1% to about 50%, preferably from about 5% to about 30%. Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol or anhydride contains from about 2 to about 18 and preferably from about 2 to about 8 carbon atoms, and each fatty acid moiety contains from about 8 to about 30 and preferably from about 12 to about 20 carbon atoms. Typically, such softeners contain from about one to about 3 and preferably about 2 fatty acid groups per molecule. The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. The fatty acid portion of the ester is normally derived from fatty acids having from about 8 to about 30 and preferably from about 12 to about 22 carbon atoms. Typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid. Highly preferred optional nonionic softening agents for use in the present invention are C10-C26 acyl sorbitan esters and polyglycerol monostearate. Sorbitan esters are esterified dehydration products of sorbitol. The preferred sorbitan ester comprises a member selected from the group consisting of C10-C26 acyl sorbitan monoesters and C10-C26 acyl sorbitan diesters and ethoxylates of said esters wherein one or more of the unesterified hydroxyl groups in said esters contain from about 1 to about 6 oxyethylene units, and mixtures thereof. For the purpose of the present invention, sorbitan esters containing unsaturation (e.g., sorbitan monooleate) can be utilized. Sorbitol, which is typically prepared by the catalytic hydrogenation of glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides.
The preferred sorbitan softening agents of the type employed herein can be prepared by esterifying the “sorbitan” mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and/or fatty acid. The esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from such reactions, and the stoichiometric ratios of the reactants can be simply adjusted to favor the desired reaction product. Certain derivatives of the preferred sorbitan esters herein, especially the “lower” ethoxylates thereof (i.e., mono-, di-, and tri-esters wherein one or more of the unesterified —OH groups contain one to about twenty oxyethylene moieties (Tweens®) are also useful in the composition of the present invention. Therefore, the term “sorbitan ester” is intended to include such derivatives. For the purposes of the present invention, it is preferred that a significant amount of di- and tri-sorbitan esters are present in the ester mixture. Ester mixtures having from about 20-50% mono-ester, about 25-50% di-ester and about 10-35% of tri- and tetra-esters are preferred. Material which is sold commercially as sorbitan mono-ester (e.g., monostearate) typically contains significant amounts of di- and tri-esters. A typical analysis of commercial sorbitan monostearate indicates that it comprises about 27% mono-, about 32% di- and about 30% tri- and tetra-esters and is therefore a preferred material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are also useful. In addition, both the 1,4- and 1,5-sorbitan esters are useful herein.
Other useful alkyl sorbitan esters for use in the softening compositions herein include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-esters. Such mixtures are readily prepared by reacting the foregoing hydroxy-substituted sorbitans, particularly the 1,4- and 1,5-sorbitans, with the corresponding acid, ester, or acid chloride in a simple esterification reaction. It is to be recognized, of course, that commercial materials prepared in this manner will comprise mixtures usually containing minor proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide structures, and the like. In the present invention, it is preferred that such impurities are present at as low a level as practical. The preferred sorbitan esters employed herein can contain up to about 15% by weight of esters of the C20-C26, and higher, fatty acids, as well as minor amounts of C8, and lower, fatty esters. Glycerol and polyglycerol esters, especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-, are also preferred herein (e.g., polyglycerol monostearate with a trade name of Radiasurf 7248). Glycerol esters can be prepared from naturally occurring triglycerides by normal extraction, purification and/or interesterification processes or by esterification processes of the type set forth hereinbefore for sorbitan esters. Partial esters of glycerin can also be ethoxylated to form usable derivatives that are included within the term “glycerol esters.” Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc. The “glycerol esters” also include the polyglycerol, e.g., diglycerol through octaglycerol esters. The polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages. The mono- and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
The fabric conditioning active in the articles of the present invention may further comprise one or more fatty acids. Typically, the fatty acid is present to improve the processability of the composition, and is admixed with any material, or materials, that are difficult to process, especially as a result of having a high viscosity. The fatty acid provides improved viscosity and/or processability, without harming softening or antistatic performance of the fabric conditioning composition. Preferred fatty acids are those containing a long chain, unsubstituted alkenyl group of from about 8 to about 30 carbon atoms, more preferably from about 11 to about 18 carbon atoms. Examples of specific carboxylic acids are: oleic acid, linoleic acid, and mixtures thereof. Although unsaturated fatty acids are preferred, the unsaturated fatty acids can be used in combination with saturated fatty acids like stearic, palmitic, and/or lauric acids. Preferred carboxylic acids are oleic, linoleic, tallow fatty acids, and mixtures thereof. Another type of preferred softener is high molecular weight fatty acid containing at least 20 carbon atoms. These fatty acids can be used in combination with the quaternary softener actives or as part of the fatty acid tertiary amine salts, or mixtures of free fatty acids and fatty acid tertiary amine salts. These fatty acids normally have higher melting ranges, thus can be used to elevate the melting range of the total softener composition if necessary. Non-limiting examples of high molecular weight fatty acids useful in the present invention are arachidic acid (C20, eicosanoic acid), docosanoic acid (C22, behenic acid), tetracosanoic acid (C24, lignoceric acid), triacontanoic acid (C30, melissic acid), and mixtures thereof. Behenic acid, arachidic acid, and mixtures thereof are preferred. Behenic acid is most preferred.
Preferably, the fatty acid is added to the quaternization reaction mixture used to form the biodegradable quaternary ammonium compounds of Formulas II, III, and/or IV as described hereinbefore to lower the viscosity of the reaction mixture to less than about 1500 cps, preferably less than about 1000 cps, more preferably less than about 800 cps. The solvent level of added fatty acid is from about 5% to about 30%, preferably from about 10% to about 25%, more preferably from about 10% to about 20%. The unsaturated fatty acid can be added before the start of the quaternization reaction or, preferably, during the quaternization reaction when it is needed to reduce the viscosity which increases with increased level of quaternization. Preferably the addition occurs when at least about 60% of the product is quaternized. This allows for a low viscosity for processing while minimizing side reactions that can occur when the quaternizing agent reacts with the fatty acid. The resulting quaternized biodegradable fabric softening actives can be used without removal of the unsaturated fatty acid, and, in fact, are more useful since the mixture is more fluid and more easily handled.
In one embodiment, the coat mix comprises a low level of water. Adding too much water to a coat mix may cause the coat mix to solidify or gel. This will cause problems in the manufacturing process as the phase changed coat mix may clog pipes or no longer have desirable flow characteristics for processing. In one embodiment, the coat mix comprises less than about 10%, alternatively less than about 9%, or 8%, or 7%, or 6%, or 5%, or 4%, or 3%, or 2%, or 1%, or 0.5%, or about 0.1% of water by weight of the coat mix. Alternatively the coat mix may comprise at least about 0.001% water, by weight of the coat mix. Alternatively the coat mix is free or substantially free of water.
The fluid fabric enhancer compositions disclosed herein comprise a fabric softening active (“FSA”). Suitable fabric softening actives, include, but are not limited to, materials selected from the group consisting of quaternary ammonium compounds, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, clays, polysaccharides, fatty acids, softening oils, polymer latexes and mixtures thereof.
Non-limiting examples of water insoluble fabric care benefit agents include dispersible polyethylene and polymer latexes. These agents can be in the form of emulsions, latexes, dispersions, suspensions, and the like. In one aspect, they are in the form of an emulsion or a latex. Dispersible polyethylenes and polymer latexes can have a wide range of particle size diameters (χ50) including but not limited to from about 1 nm to about 100 μm; alternatively from about 10 nm to about 10 μm. As such, the particle sizes of dispersible polyethylenes and polymer latexes are generally, but without limitation, smaller than silicones or other fatty oils.
Generally, any surfactant suitable for making polymer emulsions or emulsion polymerizations of polymer latexes can be used to make the water insoluble fabric care benefit agents of the present invention. Suitable surfactants consist of emulsifiers for polymer emulsions and latexes, dispersing agents for polymer dispersions and suspension agents for polymer suspensions. Suitable surfactants include anionic, cationic, and nonionic surfactants, or combinations thereof. In one aspect, such surfactants are nonionic and/or anionic surfactants. In one aspect, the ratio of surfactant to polymer in the water insoluble fabric care benefit agent is about 1:100 to about 1:2; alternatively from about 1:50 to about 1:5, respectively. Suitable water insoluble fabric care benefit agents include but are not limited to the examples described below.
Quats—Suitable quats include but are not limited to, materials selected from the group consisting of ester quats, amide quats, imidazoline quats, alkyl quats, amidoester quats and mixtures thereof. Suitable ester quats include but are not limited to, materials selected from the group consisting of monoester quats, diester quats, triester quats and mixtures thereof. In one aspect, a suitable ester quat is bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester having a molar ratio of fatty acid moieties to amine moieties of from 1.85 to 1.99, an average chain length of the fatty acid moieties of from 16 to 18 carbon atoms and an iodine value of the fatty acid moieties, calculated for the free fatty acid, which has an Iodine Value of between 0-140, preferably 5-100, more preferably 10-80, even more preferably 15-70, even more preferably 18-55, most preferably 18-25. When a soft tallow quaternary ammonium compound softener is used, most preferably range is 25-60. In one aspect, the cis-trans-ratio of double bonds of unsaturated fatty acid moieties of the bis (2 hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester is from 55:45 to 75:25, respectively. Suitable amide quats include but are not limited to, materials selected from the group consisting of monoamide quats, diamide quats and mixtures thereof. Suitable alkyl quats include but are not limited to, materials selected from the group consisting of mono alkyl quats, dialkyl quats, trialkyl quats, tetraalkyl quats and mixtures thereof.
Amines—Suitable amines include but are not limited to, materials selected from the group consisting of amidoesteramines, amidoamines, imidazoline amines, alkyl amines, amidoester amines and mixtures thereof. Suitable ester amines include but are not limited to, materials selected from the group consisting of monoester amines, diester amines, triester amines and mixtures thereof. Suitable amido quats include but are not limited to, materials selected from the group consisting of monoamido amines, diamido amines and mixtures thereof. Suitable alkyl amines include but are not limited to, materials selected from the group consisting of mono alkylamines, dialkyl amines quats, trialkyl amines, and mixtures thereof.
In one embodiment, the fabric softening active is a quaternary ammonium compound suitable for softening fabric in a rinse step. In one embodiment, the fabric softening active is formed from a reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and in one embodiment, tri-ester compounds. In another embodiment, the fabric softening active comprises one or more softener quaternary ammonium compounds such, but not limited to, as a monoalkyquaternary ammonium compound, dialkylquaternary ammonium compound, a diamido quaternary compound, a diester quaternary ammonium compound, or a combination thereof.
In one aspect, the fabric softening active comprises a diester quaternary ammonium or protonated diester ammonium (hereinafter “DQA”) compound composition. In certain embodiments of the present invention, the DQA compound compositions also encompass diamido fabric softening actives and fabric softening actives with mixed amido and ester linkages as well as the aforementioned diester linkages, all herein referred to as DQA.
In one aspect, said fabric softening active may comprise, as the principal active, compounds of the following formula:
{R4-m—N+—[X—Y—R1]m}X− (1)
wherein each R comprises either hydrogen, a short chain C1-C6, in one aspect a C1-C3 alkyl or hydroxyalkyl group, for example methyl, ethyl, propyl, hydroxyethyl, and the like, poly(C2-3 alkoxy), polyethoxy, benzyl, or mixtures thereof; each X is independently (CH2)n, CH2—CH(CH3)— or CH—(CH3)—CH2—; each Y may comprise —O—(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR—; each m is 2 or 3; each n is from 1 to about 4, in one aspect 2; the sum of carbons in each R1, plus one when Y is —O—(O)C— or —NR—C(O)—, may be C12-C22, or C14-C20, with each R1 being a hydrocarbyl, or substituted hydrocarbyl group; and X− may comprise any softener-compatible anion. In one aspect, the softener-compatible anion may comprise chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate. In another aspect, the softener-compatible anion may comprise chloride or methyl sulfate.
In another aspect, the fabric softening active may comprise the general formula:
[R3N+CH2CH(YR1)(CH2YR1)]X−
wherein each Y, R, R1, and X− have the same meanings as before. Such compounds include those having the formula:
[CH3]3N(+)[CH2CH(CH2O(O)CR1)O(O)CR1]Cl(−) (2)
wherein each R may comprise a methyl or ethyl group. In one aspect, each R1 may comprise a C15 to C19 group. As used herein, when the diester is specified, it can include the monoester that is present.
These types of agents and general methods of making them are disclosed in U.S. Pat. No. 4,137,180. An example of a suitable DEQA (2) is the “propyl” ester quaternary ammonium fabric softener active comprising the formula 1,2-di(acyloxy)-3-trimethylammoniopropane chloride.
A third type of useful fabric softening active has the formula:
[R4-m—N+—R1m]X− (3)
wherein each R, R1, m and X− have the same meanings as before.
In a further aspect, the fabric softening active may comprise the formula:
wherein each R, R1, and A− have the definitions given above; R2 may comprise a C1-6 alkylene group, in one aspect an ethylene group; and G may comprise an oxygen atom or an —NR— group;
In a yet further aspect, the fabric softening active may comprise the formula:
wherein R1, R2 and G are defined as above.
In a further aspect, the fabric softening active may comprise condensation reaction products of fatty acids with dialkylenetriamines in, e.g., a molecular ratio of about 2:1, said reaction products containing compounds of the formula:
R1—C(O)—NH—R2—NH—R3—NHC(O)—R1 (6)
wherein R1, R2 are defined as above, and R3 may comprise a C1-6 alkylene group, in one aspect, an ethylene group and wherein the reaction products may optionally be quaternized by the additional of an alkylating agent such as dimethyl sulfate. Such quaternized reaction products are described in additional detail in U.S. Pat. No. 5,296,622.
In a yet further aspect, the fabric softening active may comprise the formula:
[R1—C(O)—NR—R2—N(R)2—R3—NR—C(O)R1]+A− (7)
wherein R, R1, R2, R3 and A− are defined as above;
In a yet further aspect, the fabric softening active may comprise reaction products of fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1, said reaction products containing compounds of the formula:
R1—C(O)—NH—R2—N(R3OH)—C(O)—R1 (8)
wherein R1, R2 and R3 are defined as above;
In a yet further aspect, the fabric softening active may comprise the formula:
wherein R, R1, R2, and A− are defined as above.
In yet a further aspect, the fabric softening active may comprise the formula:
wherein;
Non-limiting examples of fabric softening actives comprising formula (1) are N,N-bis(stearoyl-oxy-ethyl)-N,N-dimethylammonium chloride, N,N-bis(tallowoyl-oxy-ethyl)-N,N-dimethylammonium chloride, N,N-bis(stearoyl-oxy-ethyl)-N-(2 hydroxyethyl)-N-methylammonium methylsulfate.
Non-limiting examples of fabric softening actives comprising formula (2) is 1,2-di-(stearoyl-oxy)-3-trimethyl ammoniumpropane chloride.
Non-limiting examples of fabric softening actives comprising formula (3) include dialkylenedimethylammonium salts such as dicanoladimethylammonium chloride, di(hard)tallowdimethylammonium chloride, dicanoladimethylammonium methylsulfate, and mixtures thereof. An example of commercially available dialkylenedimethylammonium salts usable in the present invention is dioleyldimethylammonium chloride available from Witco Corporation under the trade name Adogen® 472 and dihardtallow dimethylammonium chloride available from Akzo Nobel Arquad 2HT75.
A non-limiting example of fabric softening actives comprising formula (4) is 1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group, R5 is a methyl group and A− is a methyl sulfate anion, available commercially from the Witco Corporation under the trade name Varisoft®.
A non-limiting example of fabric softening actives comprising formula (5) is 1-tallowylamidoethyl-2-tallowylimidazoline wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, and G is a NH group.
A non-limiting example of a fabric softening active comprising formula (6) is the reaction products of fatty acids with diethylenetriamine in a molecular ratio of about 2:1, said reaction product mixture containing N,N″-dialkyldiethylenetriamine with the formula:
R1—C(O)—NH—CH2CH2—NH—CH2CH2—NH—C(O)—R1
wherein R1 is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021, available from Henkel Corporation, and R2 and R3 are divalent ethylene groups.
In one aspect, said fatty acid may be obtained, in whole or in part, from a renewable source, via extraction from plant material, fermentation from plant material, and/or obtained via genetically modified organisms such as algae or yeast.
A non-limiting example of Compound (7) is a di-fatty amidoamine based softener having the formula:
[R1—C(O)—NH—CH2CH2—N(CH3)(CH2CH2OH)—CH2CH2—NH—C(O)—R1]+CH3SO4−
wherein R1 is an alkyl group. An example of such compound is that commercially available from the Witco Corporation e.g. under the trade name Varisoft® 222LT.
An example of a fabric softening active comprising formula (8) is the reaction products of fatty acids with N-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1, said reaction product mixture containing a compound of the formula:
R1—C(O)—NH—CH2CH2—N(CH2CH2OH)—C(O)—R1
wherein R1—C(O) is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021, available from Henkel Corporation.
An example of a fabric softening active comprising formula (9) is the diquaternary compound having the formula:
wherein R1 is derived from fatty acid. Such compound is available from Witco Company.
A non-limiting example of a fabric softening active comprising formula (10) is a dialkyl imidazoline diester compound, where the compound is the reaction product of N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropyl)-1,2-ethylenediamine with glycolic acid, esterified with fatty acid, where the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydrogenated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid or a mixture of the above.
It will be understood that combinations of softener actives disclosed above are suitable for use in this invention.
In the cationic nitrogenous salts herein, the anion A−, which comprises any softener compatible anion, provides electrical neutrality. Most often, the anion used to provide electrical neutrality in these salts is from a strong acid, especially a halide, such as chloride, bromide, or iodide. However, other anions can be used, such as methylsulfate, ethylsulfate, acetate, formate, sulfate, carbonate, fatty acid anions and the like. In one aspect, the anion A may comprise chloride or methylsulfate. The anion, in some aspects, may carry a double charge. In this aspect, A− represents half a group.
In one embodiment, the fabric softening agent is chosen from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, dihydrogenatedtallow dimethyl ammonium chloride, ditallowoyloxyethyl methylhydroxyethylammonium methyl sulfate, dihydrogenated-tallowoyloxyethyl methyl hydroxyethylammonium chloride, or combinations thereof.
One aspect of the invention provides a fabric enhancer composition comprising a cationic starch as a fabric softening active. In one embodiment, the fabric care compositions of the present invention generally comprise cationic starch at a level of from about 0.1% to about 7%, alternatively from about 0.1% to about 5%, alternatively from about 0.3% to about 3%, and alternatively from about 0.5% to about 2.0%, by weight of the composition. Suitable cationic starches for use in the present compositions are commercially-available from Cerestar under the trade name C*BOND® and from National Starch and Chemical Company under the trade name CATO® 2A,
Nonionic fabric care benefit agents can comprise sucrose esters, and are typically derived from sucrose and fatty acids. Sucrose ester is composed of a sucrose moiety having one or more of its hydroxyl groups esterified.
Sucrose is a disaccharide having the following formula:
Alternatively, the sucrose molecule can be represented by the formula: M(OH)8, wherein M is the disaccharide backbone and there are total of 8 hydroxyl groups in the molecule.
Thus, sucrose esters can be represented by the following formula:
M(OH)8-x(OC(O)R1)x
wherein x is the number of hydroxyl groups that are esterified, whereas (8-x) is the hydroxyl groups that remain unchanged; x is an integer selected from 1 to 8, alternatively from 2 to 8, alternatively from 3 to 8, or from 4 to 8; and R1 moieties are independently selected from C1-C22 alkyl or C1-C30 alkoxy, linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted.
In one embodiment, the R1 moieties comprise linear alkyl or alkoxy moieties having independently selected and varying chain length. For example, R1 may comprise a mixture of linear alkyl or alkoxy moieties wherein greater than about 20% of the linear chains are C18, alternatively greater than about 50% of the linear chains are C18, alternatively greater than about 80% of the linear chains are C18.
In another embodiment, the R1 moieties comprise a mixture of saturate and unsaturated alkyl or alkoxy moieties; the degree of unsaturation can be measured by “Iodine Value” (hereinafter referred as “IV”, as measured by the standard AOCS method). The IV of the sucrose esters suitable for use herein ranges from about 1 to about 150, or from about 2 to about 100, or from about 5 to about 85. The R1 moieties may be hydrogenated to reduce the degree of unsaturation. In the case where a higher IV is preferred, such as from about 40 to about 95, then oleic acid and fatty acids derived from soybean oil and canola oil are the starting materials.
In a further embodiment, the unsaturated R1 moieties may comprise a mixture of “cis” and “trans” forms about the unsaturated sites. The “cis”/“trans” ratios may range from about 1:1 to about 50:1, or from about 2:1 to about 40:1, or from about 3:1 to about 30:1, or from about 4:1 to about 20:1.
Generally, all dispersible polyolefins that provide fabric care benefits can be used as water insoluble fabric care benefit agents in the present invention. The polyolefins can be in the format of waxes, emulsions, dispersions or suspensions. Non-limiting examples are discussed below.
In one embodiment, the polyolefin is chosen from a polyethylene, polypropylene, or a combination thereof. The polyolefin may be at least partially modified to contain various functional groups, such as carboxyl, alkylamide, sulfonic acid or amide groups. In another embodiment, the polyolefin is at least partially carboxyl modified or, in other words, oxidized.
For ease of formulation, the dispersible polyolefin may be introduced as a suspension or an emulsion of polyolefin dispersed by use of an emulsifying agent. The polyolefin suspension or emulsion may comprise from about 1% to about 60%, alternatively from about 10% to about 55%, alternatively from about 20% to about 50% by weight of polyolefin. The polyolefin may have a wax dropping point (see ASTM D3954-94, volume 15.04—“Standard Test Method for Dropping Point of Waxes”) from about 20° to about 170° C., alternatively from about 50° to about 140° C. Suitable polyethylene waxes are available commercially from suppliers including but not limited to Honeywell (A-C polyethylene), Clariant (Velustrol® emulsion), and BASF (LUWAX®).
When an emulsion is employed with the dispersible polyolefin, the emulsifier may be any suitable emulsification agent. Non-limiting examples include an anionic, cationic, nonionic surfactant, or a combination thereof. However, almost any suitable surfactant or suspending agent may be employed as the emulsification agent. The dispersible polyolefin is dispersed by use of an emulsification agent in a ratio to polyolefin wax of about 1:100 to about 1:2, alternatively from about 1:50 to about 1:5, respectively.
Polymer Latexes
Polymer latex is made by an emulsion polymerization which includes one or more monomers, one or more emulsifiers, an initiator, and other components familiar to those of ordinary skill in the art. Generally, all polymer latexes that provide fabric care benefits can be used as water insoluble fabric care benefit agents of the present invention. Additional non-limiting examples include the monomers used in producing polymer latexes such as: (1) 100% or pure butylacrylate; (2) butylacrylate and butadiene mixtures with at least 20% (weight monomer ratio) of butylacrylate; (3) butylacrylate and less than 20% (weight monomer ratio) of other monomers excluding butadiene; (4) alkylacrylate with an alkyl carbon chain at or greater than C6; (5) alkylacrylate with an alkyl carbon chain at or greater than C6 and less than 50% (weight monomer ratio) of other monomers; (6) a third monomer (less than 20% weight monomer ratio) added into an aforementioned monomer systems; and (7) combinations thereof.
Polymer latexes that are suitable fabric care benefit agents in the present invention may include those having a glass transition temperature of from about −120° C. to about 120° C., alternatively from about −80° C. to about 60° C. Suitable emulsifiers include anionic, cationic, nonionic and amphoteric surfactants. Suitable initiators include initiators that are suitable for emulsion polymerization of polymer latexes. The particle size diameter (χ50) of the polymer latexes can be from about 1 nm to about 10 μm, alternatively from about 10 nm to about 1 μm, or even from about 10 nm to about 20 nm.
Fatty Acid
One aspect of the invention provides a fabric softening composition comprising a fatty acid, such as a free fatty acid. The term “fatty acid” is used herein in the broadest sense to include unprotonated or protonated forms of a fatty acid; and includes fatty acid that is bound or unbound to another chemical moiety as well as the various combinations of these species of fatty acid. One skilled in the art will readily appreciate that the pH of an aqueous composition will dictate, in part, whether a fatty acid is protonated or unprotonated. In another embodiment, the fatty acid is in its unprotonated, or salt form, together with a counter ion, such as, but not limited to, calcium, magnesium, sodium, potassium and the like. The term “free fatty acid” means a fatty acid that is not bound to another chemical moiety (covalently or otherwise) to another chemical moiety.
In one embodiment, the fatty acid may include those containing from about 12 to about 25, from about 13 to about 22, or even from about 16 to about 20, total carbon atoms, with the fatty moiety containing from about 10 to about 22, from about 12 to about 18, or even from about 14 (mid-cut) to about 18 carbon atoms.
The fatty acids of the present invention may be derived from (1) an animal fat, and/or a partially hydrogenated animal fat, such as beef tallow, lard, etc.; (2) a vegetable oil, and/or a partially hydrogenated vegetable oil such as canola oil, safflower oil, peanut oil, sunflower oil, sesame seed oil, rapeseed oil, cottonseed oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, palm kernel oil, coconut oil, other tropical palm oils, linseed oil, tung oil, etc.; (3) processed and/or bodied oils, such as linseed oil or tung oil via thermal, pressure, alkali-isomerization and catalytic treatments; (4) a mixture thereof, to yield saturated (e.g. stearic acid), unsaturated (e.g. oleic acid), polyunsaturated (linoleic acid), branched (e.g. isostearic acid) or cyclic (e.g. saturated or unsaturated α-disubstituted cyclopentyl or cyclohexyl derivatives of polyunsaturated acids) fatty acids.
Mixtures of fatty acids from different fat sources can be used.
In one aspect, at least a majority of the fatty acid that is present in the fabric softening composition of the present invention is unsaturated, e.g., from about 40% to 100%, from about 55% to about 99%, or even from about 60% to about 98%, by weight of the total weight of the fatty acid present in the composition, although fully saturated and partially saturated fatty acids can be used. As such, the total level of polyunsaturated fatty acids (TPU) of the total fatty acid of the inventive composition may be from about 0% to about 75% by weight of the total weight of the fatty acid present in the composition.
The cis/trans ratio for the unsaturated fatty acids may be important, with the cis/trans ratio (of the C18:1 material) being from at least about 1:1, at least about 3:1, from about 4:1 or even from about 9:1 or higher.
Branched fatty acids such as isostearic acid are also suitable since they may be more stable with respect to oxidation and the resulting degradation of color and odor quality.
The Iodine Value or “IV” measures the degree of unsaturation in the fatty acid. In one embodiment of the invention, the fatty acid has an IV from about 10 to about 140, from about 15 to about 100 or even from about 15 to about 60.
Another class of fatty ester fabric care actives is softening oils, which include but are not limited to, vegetable oils (such as soybean, sunflower, and canola), hydrocarbon based oils (natural and synthetic petroleum lubricants, in one aspect polyolefins, isoparaffins, and cyclic paraffins), triolein, fatty esters, fatty alcohols, fatty amines, fatty amides, and fatty ester amines Oils can be combined with fatty acid softening agents, clays, and silicones.
Clays
In one embodiment of the invention, the fabric care composition may comprise a clay as a fabric care active. In one embodiment clay can be a softener or co-softeners with another softening active, for example, silicone. Suitable clays include those materials classified geologically smectites.
Silicone
In one embodiment, the fabric softening composition comprises a silicone. Suitable levels of silicone may comprise from about 0.1% to about 70%, alternatively from about 0.3% to about 40%, alternatively from about 0.5% to about 30%, alternatively from about 1% to about 20% by weight of the composition. Useful silicones can be any silicone comprising compound. In one embodiment, the silicone polymer is selected from the group consisting of cyclic silicones, polydimethylsiloxanes, aminosilicones, cationic silicones, silicone polyethers, silicone resins, silicone urethanes, and mixtures thereof. In one embodiment, the silicone is a polydialkylsilicone, alternatively a polydimethyl silicone (polydimethyl siloxane or “PDMS”), or a derivative thereof. In another embodiment, the silicone is chosen from an aminofunctional silicone, amino-polyether silicone, alkyloxylated silicone, cationic silicone, ethoxylated silicone, propoxylated silicone, ethoxylated/propoxylated silicone, quaternary silicone, or combinations thereof.
In another embodiment, the silicone may be chosen from a random or blocky organosilicone polymer having the following formula:
[R1R2R3SiO1/2](j+2)[(R4Si(X—Z)O2/2]k[R4R4SiO2/2]m[R4SiO3/2]j
wherein:
and wherein each v in said organosilicone is an integer from 1 to about 10, in one aspect, v is an integer from 1 to about 5 and the sum of all v indices in each Q in the said organosilicone is an integer from 1 to about 30 or from 1 to about 20 or even from 1 to about 10.
In another embodiment, the silicone may be chosen from a random or blocky organosilicone polymer having the following formula:
[R1R2R3SiO1/2](j+2)[(R4Si(X—Z)O2/2]k[R4R4SiO2/2]m[R4SiO3/2]j
wherein
In one embodiment, the silicone is one comprising a relatively high molecular weight. A suitable way to describe the molecular weight of a silicone includes describing its viscosity. A high molecular weight silicone is one having a viscosity of from about 10 cSt to about 3,000,000 cSt, or from about 100 cSt to about 1,000,000 cSt, or from about 1,000 cSt to about 600,000 cSt, or even from about 6,000 cSt to about 300,000 cSt.
In one embodiment, the silicone comprises a blocky cationic organopolysiloxane having the formula:
MwDxTyQz
wherein:
M=[SiR1R2R3O1/2], [SiR1R2G1O1/2], [SiR1G1G2O1/2], [SiG1G2G3O1/2], or combinations thereof;
D=[SiR1R2O2/2], [SiR1G1O2/2], [SiG1G2O2/2] or combinations thereof;
T=[SiR1O3/2], [SiG1O3/2] or combinations thereof;
w=is an integer from 1 to (2+y+2z);
x=is an integer from 5 to 15,000;
y=is an integer from 0 to 98;
z=is an integer from 0 to 98;
R1, R2 and R3 are each independently selected from the group consisting of H, OH, C1-C32 alkyl, C1-C32 substituted alkyl, C5-C32 or C6-C32 aryl, C5-C32 or C6-C32 substituted aryl, C6-C32 alkylaryl, C6-C32 substituted alkylaryl, C1-C32 alkoxy, C1-C32 substituted alkoxy, C1-C32 alkylamino, and C1-C32 substituted alkylamino;
at least one of M, D, or T incorporates at least one moiety G1, G2 or G3; and G1, G2, and G3 are each independently selected from the formula:
wherein:
X comprises a divalent radical selected from the group consisting of C1-C32 alkylene, C1-C32 substituted alkylene, C5-C32 or C6-C32 arylene, C5-C32 or C6-C32 substituted arylene, C6-C32 arylalkylene, C6-C32 substituted arylalkylene, C1-C32 alkoxy, C1-C32 substituted alkoxy, C1-C32 alkyleneamino, C1-C32 substituted alkyleneamino, ring-opened epoxide, and ring-opened glycidyl, with the proviso that if X does not comprise a repeating alkylene oxide moiety then X can further comprise a heteroatom selected from the group consisting of P, N and O;
each R4 comprises identical or different monovalent radicals selected from the group consisting of H, C1-C32 alkyl, C1-C32 substituted alkyl, C5-C32 or C6-C32 aryl, C5-C32 or C6-C32 substituted aryl, C6-C32 alkylaryl, and C6-C32 substituted alkylaryl;
E comprises a divalent radical selected from the group consisting of C1-C32 alkylene, C1-C32 substituted alkylene, C5-C32 or C6-C32 arylene, C5-C32 or C6-C32 substituted arylene, C6-C32 arylalkylene, C6-C32 substituted arylalkylene, C1-C32 alkoxy, C1-C32 substituted alkoxy, C1-C32 alkyleneamino, C1-C32 substituted alkyleneamino, ring-opened epoxide and ring-opened glycidyl, with the proviso that if E does not comprise a repeating alkylene oxide moiety then E can further comprise a heteroatom selected from the group consisting of P, N, and O;
E′ comprises a divalent radical selected from the group consisting of C1-C32 alkylene, C1-C32 substituted alkylene, C5-C32 or C6-C32 arylene, C5-C32 or C6-C32 substituted arylene, C6-C32 arylalkylene, C6-C32 substituted arylalkylene, C1-C32 alkoxy, C1-C32 substituted alkoxy, C1-C32 alkyleneamino, C1-C32 substituted alkyleneamino, ring-opened epoxide and ring-opened glycidyl, with the proviso that if E′ does not comprise a repeating alkylene oxide moiety then E′ can further comprise a heteroatom selected from the group consisting of P, N, and O;
p is an integer independently selected from 1 to 50;
n is an integer independently selected from 1 or 2;
when at least one of G1, G2, or G3 is positively charged, A−t is a suitable charge balancing anion or anions such that the total charge, k, of the charge-balancing anion or anions is equal to and opposite from the net charge on the moiety G1, G2 or G3; wherein t is an integer independently selected from 1, 2, or 3; and k≦(p*2/t)+1; such that the total number of cationic charges balances the total number of anionic charges in the organopolysiloxane molecule; and wherein at least one E does not comprise an ethylene moiety.
The present invention can include other optional components (minor components) conventionally used in textile treatment compositions, for example, anti-oxidants, colorants, preservatives, optical brighteners, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, anti-wrinkle agents, soil release agents, fabric crisping agents, reductive agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, Color Care Agents including Chlorine Scavengers, Dye Transfer Inhibitors, Dye Fixatives Chelants and Anti-Abrasion Agents Perfume, PMC's, Cyclodextrin Perfume Complexes, Free Cyclodextrin, Pro-Perfumes; Antioxidants and the like.
One aspect of the present invention relates to fabric conditioning compositions which are delivered to fabric via dryer-added substrate that effectively releases the composition in an automatic laundry (clothes) dryer. Such dispensing means can be designed for single usage or for multiple uses. The dispensing means can also be a “carrier material” that releases the fabric conditioning composition and then is dispersed and/or exhausted from the dryer. When the dispensing means is a flexible substrate, e.g., in sheet configuration, the fabric conditioning composition is releasably affixed on the substrate to provide a weight ratio of conditioning composition to dry substrate ranging from about 10:1 to about 0.5:1, preferably from about 5:1 to about 1:1. To insure release, preferred flexible sheets withstand the dryer environment without decomposing or changing shape, e.g. combusting, creating off odors, or shrinking with heat or moisture. Substrates especially useful herein are rayon and/or polyester non-woven fabrics. Non-limiting examples of the substrates useful herein are cellulosic rayon and/or polyester non-woven fabrics having basis weights of from about 0.4 oz./yd2 to about 1 oz./yd2, preferably from about 0.5 oz./yd2 to about 0.8 oz./yd2, more preferably from about 0.5 oz./yd2 to about 0.6 oz./yd2. These substrates are typically prepared using, e.g., rayon and/or polyester fibers having deniers of from about 1 to about 8, preferably from about 3 to about 6, and more preferably about 4 to 6 or mixtures of different deniers. Typically, the fiber is a continuous filament or a 3/16 inch to 2 inch fiber segment that is laid down, in a pattern that results in a multiplicity of layers and intersections between overlayed portions of the filament or fiber, on a belt, preferably foraminous, and then the fiber intersections are glued and/or fused into fiber-to-fiber bonds by a combination of an adhesive binder, and/or heat and/or pressure. As non-limiting examples, the substrate may be spun-bonded, melt-bonded, or point bonded or combinations of bonding processes may be chosen. The substrate breaking strength and elasticity in the machine and cross direction is sufficient to enable the substrate to be conveyed through a coating process. The porosity of the substrate article is sufficient to enable air flow through the substrate to promote conditioning active release and prevent dryer vent blinding. The substrate may also have a plurality of rectilinear slits extended along one dimension of the substrate.
The dispensing means will normally carry an effective amount of fabric conditioning composition. Such effective amount typically provides sufficient softness, antistatic effect and/or perfume deposition for at least one treatment of a minimum load in an automatic laundry dryer. Amounts of the fabric conditioning composition irrespective of load size for a single article can vary from about 0.1 g to about 100 g, preferably from about 0.1 g to about 20 g, most preferably from about 0.1 g to about 10 g. Amounts of fabric treatment composition for multiple uses, e.g., up to about 30, can be used.
Malodor reduction materials may be separated from mixtures, including but not limited to finished products such as consumer products and identified, by analytical methods that include GC-MS and/or NMR.
The saturation Vapour Pressure (VP) values are computed for each PRM in the perfume mixture being tested. The VP of an individual PRM is calculated using the VP Computational Model, version 14.02 (Linux) available from Advanced Chemistry Development Inc. (ACD/Labs) (Toronto, Canada) to provide the VP value at 25° C. expressed in units of torr. The ACD/Labs' Vapor Pressure model is part of the ACD/Labs model suite.
The value of the log of the Octanol/Water Partition Coefficient (log P) is computed for each PRM in the perfume mixture being tested. The log P of an individual PRM is calculated using the Consensus log P Computational Model, version 14.02 (Linux) available from Advanced Chemistry Development Inc. (ACD/Labs) (Toronto, Canada) to provide the unitless log P value. The ACD/Labs' Consensus log P Computational Model is part of the ACD/Labs model suite.
In order to conduct the calculations involved in the computed-value test methods described herein, the starting information required includes the identity, weight percent, and molar percent of each PRM in the perfume being tested, as a proportion of that perfume, wherein all PRMs in the perfume composition are included in the calculations. Additionally for each of those PRMs, the molecular structure, and the values of various computationally-derived molecular descriptors are also required, as determined in accordance with the Test Method for the Generation of Molecular Descriptors described herein.
For each PRM in a perfume mixture or composition, its molecular structure is used to compute various molecular descriptors. The molecular structure is determined by the graphic molecular structure representations provided by the Chemical Abstract Service (“CAS”), a division of the American Chemical Society, Columbus, Ohio, U.S.A. These molecular structures may be obtained from the CAS Chemical Registry System database by looking up the index name or CAS number of each PRM. For PRMs, which at the time of their testing are not yet listed in the CAS Chemical Registry System database, other databases or information sources may be used to determine their structures. For a PRM which has potentially more than one isomer present, the molecular descriptor computations are conducted using the molecular structure of only one of the isomers, which is selected to represent that PRM. The selection of isomer is determined by the relative amount of extension in the molecular structures of the isomers. Of all the isomers of a given PRM, it is the isomer whose molecular structure that is the most prevalent which is the one that is selected to represent that PRM. The structures for other potential isomers of that PRM are excluded from the computations. The molecular structure of the isomer that is the most prevalent is paired with the concentration of that PRM, where the concentration reflects the presence of all the isomers of that PRM that are present.
A molecule editor or molecular sketching software program, such as ChemDraw (CambridgeSoft/PerkinElmer Inc., Waltham, Mass., U.S.A.), is used to duplicate the 2-dimensional molecular structure representing each PRM. Molecular structures should be represented as neutral species (quaternary nitrogen atoms are allowed) with no disconnected fragments (e.g., single structures with no counter ions). The winMolconn program described below can convert any deprotonated functional groups to the neutral form by adding the appropriate number of hydrogen atoms and will discard the counter ion.
For each PRM, the molecular sketching software is used to generate a file which describes the molecular structure of the PRM. The file(s) describing the molecular structures of the PRMs is subsequently submitted to the computer software program winMolconn, version 1.0.1.3 (Hall Associates Consulting, Quincy, Mass., U.S.A., www.molconn.com), in order to derive various molecular descriptors for each PRM. As such, it is the winMolconn software program which dictates the structure notations and file formats that are acceptable options. These options include either a MACCS SDF formatted file (i.e., a Structure-Data File); or a Simplified Molecular Input Line Entry Specification (i.e., a SMILES string structure line notation) which is commonly used within a simple text file, often with a “.smi” or “.txt” file name extension. The SDF file represents each molecular structure in the format of a multi-line record, while the syntax for a SMILES structure is a single line of text with no white space. A structure name or identifier can be added to the SMILES string by including it on the same line following the SMILES string and separated by a space, e.g.: C1=CC═CC=C1 benzene.
The winMolconn software program is used to generate numerous molecular descriptors for each PRM, which are then output in a table format. Specific molecular descriptors derived by winMolconn are subsequently used as inputs (i.e., as variable terms in mathematical equations) for a variety of computer model test methods in order to calculate values such as: saturation Vapour Pressure (VP); Boiling Point (BP); logarithm of the Octanol/Water Partition Coefficient (log P); Odour Detection Threshold (ODT); Malodour Reduction Value (MORV); and/or Universal Malodour Reduction Value (Universal MORV) for each PRM. The molecular descriptor labels used in the models' test method computations are the same labels reported by the winMolconn program, and their descriptions and definitions can be found listed in the winMolconn documentation. The following is a generic description of how to execute the winMolconn software program and generate the required molecular structure descriptors for each PRM in a composition.
Blocker materials suitable for use in consumer products of the present invention are chosen for their ability to decrease malodor, while not interfering with perception of a fragrance. Material selection is done by assigning two indices to a test sample material from two reference scales in order to rank odor strengths. The two reference scales are the Fragrance Fidelity Index (FFI) scale and the Blocker Index (BI) scale. The FFI ranks the ability of the test sample material to impart a perceivable odor which could cause interference when combined with another fragrance and the BI ranks the ability of the test sample material to reduce malodor perception. The two methods for assigning the indices to a test sample on the FFI and the BI reference scales are given below.
The first step in the method for assigning an FFI to the test samples on the FFI reference scale is to create the FFI reference swatches. The swatches for the scale are created by treating clean fabrics swatches with a known amount of a known concentration of an ethyl vanillin solution. Fabric swatches for this test are white knit polycotton (4 inch×4 inch) swatches from EMC ordered as PC 50/50. The supplier is instructed to strip the swatches first, stripping involves washing twice with a fragrance-free detergent and rinsing three times.
Make three solutions of ethyl vanillin using a 50%/50% EtOH/water as the diluent at the following concentrations: 25 ppm, 120 ppm and 1000 ppm. Pipette 13 μL of each of the three solutions into the middle of a clean swatch resulting in about a 1 cm diameter of the solution in the middle of the swatch. This will create a sensory scale of three swatches with three different odor levels based on the concentration of the solution pipetted onto the swatch. After drying for 30 minutes in a vented hood, the swatches are wrapped in aluminum foil to prevent odor contamination to the treated swatch. A clean untreated swatch is also included as the lowest anchor point of reference for odor strength on the FFI scale. The FFI reference scale swatches should be used within 0.5 to 12 hours and discarded after 12 hours. The swatches are used as scale anchor points when graders evaluate a test sample(s) and are assigned a Fragrance Fidelity Index (FFI) as show in Table 7.
At least four perfumers/expert graders are used to rank the ethyl vanillin swatches in the FFI scale. The perfumer/expert grader needs to demonstrate adequate discrimination on the scale. The perfumer/expert panel is asked to rank order swatches according to a scale between 0 and 3. The panel must demonstrate statistical differences between the swatches as seen in Table 7.
The expert graders must demonstrate a full range of 2.5 over the 4 swatches to be acceptably discriminating. Grader 2 in table 1 has a range of only 2 and is eliminated from the panel. The panel of expert graders must also demonstrated the ability to statistically discriminate between swatches in the scale.
The reference swatches represent the 0, 1, 2, and 3 FFIs on the FFI reference scale, Table 9. The expert grader should familiarize them self with the strength of the odor on the FFI reference swatches by sniffing each one starting at 0 (the lowest odor strength) and ending at 3 (the highest odor strength). This should be done prior to evaluating the test sample material treated swatch.
Making Swatches Treated with the Test Material
A clean swatch is treated with 13 μL of a known concentration of a test sample material resulting in an about 1 cm of the solution on the clean swatch. Just like the reference swatches, the test sample material swatch is dried in a vented hood for 30 minutes and then wrapped in aluminum foil to prevent contamination. The test material swatches and the FFI reference swatches should be made within 2 hours of each other. The test material swatch must be used within 0.5 to 12 hours and discarded after 12 hours.
At least two perfumers/expert graders are used to assign an FFI grade to a test sample. The perfumer/expert grader smells the test sample swatch by holding that swatch 1 inch from their nose with their nose centered over the area where the test sample was pipetted on to the fabric and then assigns the test sample an FFI grade using the FFI reference scale anchor swatches as references. The test sample swatch is assigned an FFI grade at or between numbers on the FFI scale shown in Table 9. In cases where the test sample material is graded greater than 3, the test material is not a blocker material or the concentration of the material needs to be lowered and reevaluated to determine if a lower level has a malodor blocker functionality.
The first step in the method for assigning a BI to a test sample material on the BI reference scale is to create the BI reference swatches. The swatches for the scale are created by treating clean fabrics swatches with a known amount of a known volume of isovaleric acid solution at a known concentration. Fabric swatches for this test are white knit polycotton (4 inch×4 inch) swatches from EMC ordered as PC 50/50. The supplier is instructed to strip the swatches first, stripping involves washing twice with a fragrance-free detergent and rinsing three times.
Make one solution of 0.08% isovaleric acid using 50%/50% EtOH/water as the diluent. The BI scale contains one clean swatch with no malodor applied. Three other swatches each have a different volume of the 0.08% isovaleric acid applied. Pipette 2 μL of the 0.08% isovaleric acid solution to one clean swatch, 5 μL of the 0.08% isovaleric acid solution to the next swatch and 20 μL of isovaleric acid to the final clean swatch. These solutions are pipetted to the middle of the swatches. This will create a sensory scale of three swatches with three different odor levels based on the volume of the 0.08% isovaleric acid solution pipetted onto the swatch. After drying for 30 minutes in a vented hood, the swatches are wrapped in aluminum foil to prevent odor contamination to the treated swatch. A clean untreated swatch is also included as the lowest anchor point of reference for malodor strength on the BI scale. The BI reference scale swatches should be used within 0.5 to 12 hours and discarded after 12 hours. The swatches are used as scale anchor points when graders evaluate a test sample(s) and are assigned a Blocker Index (BI) as show in Table 12.
At least four perfumers/expert graders are used to rank the isovaleric acid swatches in the BI scale. The perfumer/expert grader needs to demonstrate adequate discrimination on the scale. The perfumer/expert grader is asked to rank order swatches according to a scale between 0 and 3. The panel of graders must demonstrate statistical differences between the swatches as seen in Table 10.
The expert graders must demonstrate a full range of 2.5 over the 4 swatches to be acceptably discriminating. The panel of expert graders must also demonstrated the ability to statistically discriminate between swatches in the scale. Expert grader #2 did not demonstrate the ability to discriminate between the swatches and is eliminated from the panel, see Table 11.
The reference swatches represent the 0, 1, 2, and 3 BIs on the BI reference scale, Table 12. The expert grader should familiarizes him/herself with the strength of the odor on the BI reference swatches by sniffing each one starting at 0 (the lowest odor strength) and ending at 3 (the highest odor strength). This should be done prior to evaluating the swatch treated with the test material.
Making the Malodorous Swatch and Treating it with a Test Material
To evaluate the BI, the test material is applied to a malodorous swatch to determine how well the test material blocks the malodor. The malodorous swatch is made by treating a clean swatch with 20 μL of a 0.08% solution of isovaleric acid. Dry the malodorous swatch treated with isovaleric acid in a vented hood for 30 minutes. After drying the malodorous swatch a known concentration of test material solution, between 1 ppm and 100 ppm is pipetted onto the malodorous swatch. Apply the test material solution right on top of the spot where the isovaleric acid solution was applied making an about 1 cm diameter spot. Just like the BI reference swatches, the isovaleric acid+test material swatch is dried in a vented hood for 30 minutes and then wrapped in aluminum foil to prevent contamination. The isovaleric acid+test material swatches and the BI reference swatches should be made within 2 hours of each other. The isovaleric acid+test material swatch must be used between 1-12 hours just like the reference swatches. It is sometimes necessary to evaluate several levels of the test material between about 1 and about 100 ppm to determine the BI.
At least two perfumers/expert graders are used to assign the BI to the test sample. The expert grader smells the isovaleric acid+test material swatch by holding that swatch one inch from their nose with their nose centered over the area where the test sample was pipetted on to the fabric and then assigns the isovaleric acid+test material swatch a BI based on ranking its odor strength against the odor strength of the swatches in the BI reference scale. The test sample swatch is assigned a BI at or between numbers on the BI in table. In cases where the isovaleric acid+test material swatch odor is greater than 3 on the BI reference scale, this indicates the material is not a blocker or the concentration of the test material needs to be lowered to achieve its blocker functionality.
Malodor Reduction Compounds with FFI and BI Grades Based on the Aforementioned
Malodor Control Compounds with Improved Performance at Lower Levels.
Below are some non-limiting examples of preferred behavior by which the malodor control compound gives improved malodor control at lower concentration. These nonlimiting data provide additional compelling data that malodor is being blocked, not masked.
The example below demonstrates that while a malodor control compound could fail to demonstrate odor blocking (BI>2.5) at a higher concentration it should be retested at a lower concentration to determine if it passes.
In the present invention blends enable more potent malodor reduction because blends are useful at a higher % of the product composition before becoming olfactively noticeable. Below are non-limiting examples of malodor reduction compounds.
An example of a dryer added fabric softener sheet composition prepared with malodor reduction composition, according to the compositions shown in Example 1.
1DEQA1: Di(soft tallowoyloxyethyl)dimethylammonium methyl sulfate with 25% > 7018 FA, as described below, as solvent
2DEQA2: Di(soft tallowoyloxyethyl)hydroxyethylmethylammonium methyl sulfate with 18% partially hydrogenated tallow fatty acid solvent
2DTDMAMS: Di(hydrogenated tallowalkyl)dimethylammoniun methyl sulfate
47018FA: 70:30 Stearic Acid:Palmitic Acid (IV = 0) Industrene 7018 sold by Witco
5TS-20: Polyoxyethylene-20 Sorbitan Tristearate (Glycosperse TS-20, sold by Lonza
6SMS: Sorbitan Mono Sterate
7SDASA: 1:2 ratio of stearyl dimethyl amine:triple passed stearic acid
8TPED: N,N,N′, N′-Tetrakis(2-hydroxypropyl)ethylenediamine (Quadrol, sold by BASF)
9Complex: Beta-Cyclodextrin/Perfume Complex
10Clay: Calcium Bentonite Clay (Bentonite L sold by Southern Clay Products Free (Neat) Perfume
11PMC: is a friable shell. About 50% water by weight of the PMC (including encapsulated perfume and/ or blocker) is assumed. The micro capsule encapsulates perfume, malodor reduction composition, or combinations thereof with the total internal phase at about 32% active.
The compositions of Example 6 are mixed homogeneously and impregnated onto a non-woven polyester sheet having dimensions of about 6% in×12″ (about 17.1 cm×30.5 cm) and weighing about 1 gram.
The resulting dryer added fabric softener sheet product when added to an automatic dryer is effective at reducing malodor on the clothing.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests, or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is, therefore, intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
| Number | Date | Country | |
|---|---|---|---|
| 62055844 | Sep 2014 | US | |
| 62143862 | Apr 2015 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14865099 | Sep 2015 | US |
| Child | 15432957 | US |
