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MXPA98007738A - Composition concentrated fabric softener conveyor recovery of freezing / defrosting and composite fabric softener highly unsaturated for im - Google Patents

Composition concentrated fabric softener conveyor recovery of freezing / defrosting and composite fabric softener highly unsaturated for im

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Publication number
MXPA98007738A
MXPA98007738A MXPA/A/1998/007738A MX9807738A MXPA98007738A MX PA98007738 A MXPA98007738 A MX PA98007738A MX 9807738 A MX9807738 A MX 9807738A MX PA98007738 A MXPA98007738 A MX PA98007738A
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MX
Mexico
Prior art keywords
active ingredient
group
composition
carbon atoms
mixtures
Prior art date
Application number
MXPA/A/1998/007738A
Other languages
Spanish (es)
Inventor
Hoffman Wahl Errol
Trinh Toan
Bernardo Tordil Helen
Joseph Harvey George
Original Assignee
The Procter & Gamble Company
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Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Publication of MXPA98007738A publication Critical patent/MXPA98007738A/en

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Abstract

Biodegradable fabric softening compounds are disclosed which contain ester bonds and a substantial level of polyunsaturates in the hydrophobic chains, the compounds can be used to form fabric softening compositions which are aqueous dispersions of the compounds, these compositions have a desirable low viscosity and are recover after freezing and thawing to have a low viscosity

Description

CONCENTRATED COMPOSITION SMOOTHING DB FABRICS WITH GOOD RECOVERY OF CONCERNING / DEFROSTING AND COMPOSITE SOFTENER DB TO S A TA ENTE INSATURADQ Pft? fr SAME TECHNICAL FIELD The present invention relates to highly unsaturated biodegradable fabric softening compounds, for use in the preparation of softening compounds, useful for softening fabrics. It relates especially to the preparation of concentrated textile softening compositions with good freeze / thaw recovery properties for use in the rinse cycle of a domestic textile washing operation, to give excellent fabric softening / control benefits of static and rewetting.
BACKGROUND OF THE INVENTION Fabric softening compositions containing high levels of softener are known in the art. However, there is a need for highly concentrated compositions having good freeze / thaw recovery properties, especially compositions that can be prepared by processing at normal ambient temperatures. The present invention provides aqueous, highly concentrated liquid compositions for treatment of textiles, which have improved stability (ie, do not precipitate, gel, thicken or solidify) at normal temperatures, i.e. environmental, and at temperatures below normal, under conditions of prolonged storage, and which will recover after freezing, to form stable compositions.
BRIEF DESCRIPTION DB tA INVENTION The liquid fabric softening compositions, herein, comprise: A. about 15% to 50%, preferably about 16% to 35%, better still, about 17% to 30% by weight of the composition, A fabric softening active ingredient, biodegradable, selected from the group consisting of: 1. Softener that has the formula: (-) [~ [.R.4-m-N (+) - [(H2) n -? - Rl] m] X (1) wherein each R substituent is a short chain alkyl or hydroxyalkyl group of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, for example, methyl (most preferred), ethyl, propyl, hydroxyethyl and the like; benzyl or its mixtures; each m is 2 or 3; each n is from 1 to around 4; each Y is 0- (0) -C-, or -C (0) -0-; the sum of carbons in each R plus one when Y is -0- (0) C- is from 12 to 22 carbon atoms, preferably from 14 to 20 carbon atoms, each R1 being a hydrocarbyl or substituted hydrocarbyl group, Preference is given to alkyl, mono-unsaturated alkylene and polyunsaturated alkylene groups, the softening active ingredient containing polyunsaturated alkylene groups being at least about 3%, preferably at least about 5%, better still, at least about 10%, and still more preferable, at least about 15% by weight of the total softener active ingredient present (as used herein, the "softener active ingredient percentage" which contains a given R1 group is equal to the percentage of that same group R1 with respect to to the total R1 groups used to form all the softening active ingredients), - (as used herein, the iodine value of an "original" fatty acid or a "corresponding" fatty acid is used to define a level of unsaturate for a group R1 that is equal to the level of unsaturation that would be present in the fatty acid containing the same group R1); and wherein the counter ion X "can be any anion compatible with the softener, preferably chloride, bromide, methylsulfate or nitrate, more preferably, chloride; 2. softener having the formula: wherein each Y, R, R1 and X ^ - 'have the same meanings as before (said compounds include those having the formula: [CH3] 3N (+) [CH2CH (CH20C [03R1) 0C (0) R1CL (.). especially when CÍOJR1 is derived from mixtures of groups R1, which contain some saturated fatty acid, some unsaturated fatty acid, for example, oleic, and some polyunsaturated fatty acid; and preferably, each R is a methyl or ethyl group and, preferably, each R is on the scale of 15 to 19 carbon atoms, with varying degrees of unsaturation present in the alkyl chains), - and 3. its mixtures; said fabric softening active ingredient being in the form of a stable dispersion, -B. Optionally, from 0% to about 10%, preferably from about 0.1% to 5% and, better yet, about 0.2% to 3% , of perfume, - C. Optionally, from 0% to 2%, preferably around 0.01% to 0.2% and, better yet, about 0.035% to 0.1% stabilizer, - and D. the remainder being a liquid carrier comprising water and, optionally, about 5% to 30%, preferably about 8% to 25%, better yet, about 10% to 20%, by weight of the composition, of water-soluble organic solvent, - the viscosity of the composition being less than about 500 cps, preferably less than about 400 cps, better still, less than about 200 cps, and recovering at less than about 1,000 cps, preferably less than about 500 cps , better still, less than around 200 cps, after freezing and thawing. The pH of the compositions should be about 1 to 5, preferably about 1.5 to 4.5, better still, about 2 to 3.5.
DETAILED DESCRIPTION DB THE INVENTION A, EL ureRB iB TE ACTIVE SVAVIZAPOR PB FABRICS The essential component here is about 15% to 50%, preferably about 16% to 35%, better still, about 17% to 30% by weight of the composition, of a biodegradable active ingredient, fabric softener , selected from the compounds identified below, and their mixtures. These compounds are novel compounds that have non-obvious properties when formulated to concentrated aqueous fabric softener compositions of the traditional type, which are dispersions / suspensions of fabric softening active ingredients. The compounds should have at least about 3%, preferably at least about 5%, better still, at least about 10% and, even more especially, at least about 15% polyunsaturated groups containing softening active ingredient . This polyunsaturation provides superior freeze / thaw recovery. Normally polyunsaturated groups would not be desired in the active ingredients, since they tend to be much more unstable than when there are equal monounsaturated groups. The presence of these strongly unsaturated materials makes it highly desirable, and for the highest levels of polyunsaturation, essential, that the compounds and / or compositions herein contain antibacterial, antioxidant and / or reducing materials, to protect the active ingredients against Degradation.
THE COMPOSITE ACTIVE SOFTENER OF DIESTER AND AMMONIUM FABRICS QUATERNARY (PBQA) (1) The first type of DEQA comprises, preferably, as the main active ingredient, compounds of the formula: [() 4-m-N (+) - [(CH2) N-7-R1] m] X (") ~ \ (1) wherein each R substituent is a short chain alkyl or hydroxyalkyl group of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, for example, methyl (most preferred), ethyl, propyl, hydroxyethyl and the like; benzyl or its mixtures; each m is 2 or 3; each n is from 1 to around 4; each Y is 0- (0) -C-, or -C (0) -0-, - the sum of carbons in each R1 plus one when Y is -0- (0) C- is 12 to 22 atoms carbon, preferably 14 to 20 carbon atoms, each R1 being a hydrocarbyl or substituted hydrocarbyl group. Preferably, the softening active ingredient contains alkyl, mono-unsaturated alkylene and polyunsaturated alkylene groups, the softening active ingredient containing polyunsaturated alkylene groups being at least about 3%, preferably at least about 5%, better still, so less about 10% and more especially at least about 15% by weight of the total softener active ingredient present. (As used herein, the "softener active ingredient percentage" which contains a given R1 group is based on taking a percentage of the total active ingredient, based on the percentage in which the given R1 group is present, with respect to the total of group R1). The iodine value (hereinafter referred to in the present VY) of the original fatty acids of these groups R1, preferably is around 60 to 140, better yet, about 709 to 130, still better, about 75 to 115 , on average. It is believed that the active ingredients comprising unsaturated R1 groups are preferably about 50% to 100%, preferably about 55% to 95%, and better still, about 60% to 90% by weight, of the total ingredient active present. The active ingredients containing the polyunsaturated R1 groups are at least about 3%, preferably at least about 5%, better still, at least about 10_% and more especially, at least about 15% by weight of the total of the active ingredients present. These polyunsaturated groups are necessary to provide optimum viscosity stability, especially after freezing and thawing. The higher the level of unsaturated R1 groups in the active ingredients, the lower may be the level of active ingredients comprising the unsaturated R groups. The opposite ion X ^ "^ above can be any anion compatible with the softener, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, sulfate, nitrate and the like and, more preferably, chloride. of biodegradable quaternary ammonium fabrics preferably contain the CfOlR1 group which is derived, primarily from unsaturated fatty acids, for example, oleic acid, the essential polyunsaturated fatty acids and / or saturated fatty acids and / or partially hydrogenated fatty acids from natural, for example, derived from vegetable oils and / or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soy bean oil, oil derived from first distillation, rice bran oil, etc. In other preferred embodiments, the fatty acids have the following approximate distributions, being similar of the DEQA compared to those described in the technique: Acyl group DEQA1 DEQA2 DEQA3 DEQA4 DEQA5 fatty C12 vestigial trace 0 0 0 C14 3 3 0 0 0 C16 4 4 5 5 5 C18 0 0 5 6 6 C14: l 3 3 0 0 0 C16: l 11 7 0 0 0 C18: l 74 73 71 68 67 C18: 2 4 8 81 11 1 C18: 3 0 1 1 2 2 C20_l 0 0 2 2 2 Acyl group DEQA1 DEQA2 DEQA3 DEQA4 DEQA5 fatty C20 and more 0 0 2 0 0 Unknown 0 0 6 6 7 TOTAL 99 99 100 100 102 VI 86-90 88-95 99 100 95 cis / trans 20-30 20-30 4 5 5 TPU 4 9 10 13 13 The following are non-limiting examples of DEQA: Fatty acrylic group DEQAi? DEQ C14 0 1 C16 11 25 C18 4 20 C14: 1 0 C16: 1 1 C18: 1 27 45 C18: 2 50 6 C18: 3 7 0 Unknown 0 3 TOTAL 100 100 V AND 125-128 56 cis-trans ( C18: D not available 7 TPU 57 6 DEQA10 is prepared from soybean fatty acid and DEQA11 is prepared from hydrogenated tallow fatty acid.
It is preferred that at least a majority of the fatty acyl groups be saturated, for example, about 50% to 100%, preferably about 55% to 95%, better still, about 60% to 90% and that the Total level of active ingredients containing polyunsaturated fatty acyl groups (TPU) is about 3% to 30%, preferably about 5% to 25%, even better, about 10% to 18%. The cis / trans ratio for the unsaturated fatty acyl groups is important, with a cis / trans ratio of 1: 1 to around 50: 1, the minimum being 1: 1, preferably at least 3: 1 and, better yet, around 4: 1 to around 20: 1. Unsaturated fatty acyl groups, including polyunsaturates, provide surprisingly, but also provide better rewetting characteristics, good antistatic characteristics and superior recovery after freezing and thawing. Highly unsaturated materials are also easier to formulate into concentrated premixes that maintain their low viscosity and, therefore, are easier to process, for example, pump, mix, etc. These strongly unsaturated materials, with only a low amount of solvent, which is normally associated with said materials, ie, around 5% to 20%, preferably around 8% to 2%, better yet, about 10% a 20% by weight of total softener / solvent mixture, also make formulation easier to concentrated stable dispersion compositions of the present invention, even at ambient temperatures. This ability to process active ingredients at low temperatures is especially important for polyunsaturated groups, since it minimizes degradation. Additional protection against degradation may be provided when the compounds and softening compositions contain antioxidants and / or effective reducing agents, as described below. It will be understood that the R and R substituents may be optionally substituted with various groups, such as alkoxy or hydroxyl groups, as long as the R groups retain their essentially hydrophobic nature. Preferred compounds can be considered as variations of biodegradable diester of the ditallow dimethyl ammonium chloride (hereinafter referred to as "DTDMAC"), which is a widely used fabric softener. A preferred long-chain DEQA is DEQA prepared from sources containing high levels of polyunsaturation, ie, N, N-di (acyl-oxyethyl) -N, N-dimethylammonium chloride, wherein the acyl is derived from fatty acids that contain sufficient polyunsaturation. As used herein, when the diester is specified, it may include the monoester that is present. Preferably at least about 80% of the DEQA is in the diester form, and from 0% to about 20% can be a monoester of DEQA (e.g., in the formula (1), m is 2 and a YR group is "H" or "-C- (0) -0H"). To soften, under conditions of no washed detergent or low detergent carried, the percentage of monoester should be as low as possible, preferably no more than about 5%. Nevertheless, under conditions of high carryover of anionic detergent surfactant or builder, some monoester may be preferred. The general proportions of diester to monoester are about 100: 1 to 2: 1, preferably about 50: 1 to 5: 1, better still, about 13: 1 to 8: 1. Under conditions of heavy detergent carryover, the di / monoester ratio is preferably about 11: 1. The level of monoester present can be controlled in the manufacture of DEQA. The above compounds, used as the quaternized, biodegradable ester-amine softening material, in the practice of this invention can be prepared using normal reaction chemistry. In a synthesis of a diester variation of the DTDMAC, an amine of the formula RN (CH2CH20H) 2 in both hydroxyl groups is esterified with an acid chloride of the formula R1C (0) C1, then quaternized with an alkyl halide , RX, to produce the desired reaction product (wherein R and R1 are as defined herein above). However, those skilled in the chemical arts will appreciate that this reaction sequence allows a broad selection of agents to be prepared. Another DEQA softening active ingredient, which is suitable for the formulation of the concentrated liquid fabric softening compositions of the present invention, has the above formula (I) wherein the R group is a hydroxyalkyl group of 1 to 4 carbon atoms. carbon, preferably one in which a group R is a hydroxyethyl group. An example of said hydroxyethyl ester active ingredient is di (acyloxyethyl) (2-hydroxyethyl) methylammonium methylsulfate, wherein the acyl is derived from the fatty acids described hereinbefore. Another example of this type of DEQA is derived from the same fatty acid as that of DEQA1, and is designated hereinafter as DEQA8. (2) A second type of active ingredient DEQA has the general formula: in which each of Y, R, R and x '~' has the same meanings as before. Said compounds include those having the formula: [CH3] 3N (") [CH2CH (CH20C [0] R1) OC (0) R1] Cl (" wherein each R is a methyl or ethyl group and, preferably, each R1 is on the scale of 15 to 19 carbon atoms. As used herein, when the diester is specified, it may include the monoester that is present. The amount of monoester that may be present is the same as in DEQA'1 ^. These types of agents and the general methods for preparing them are described in US Patent No. 4,137,180, by Naik and co-inventors, issued January 30, 1979, which is incorporated herein by reference. An example of a preferred DEQA of formula (2) is the fabric softener active ingredient of "propyl" quaternary ammonium ester, having the formula 1,2-di (acyloxy) -3-trimethylammoniopropane chloride, wherein the acyl is the same as that of DEQA5, and is designated hereafter as DEQA9. The DEQA active ingredients described above may contain a low level of the fatty acids which may be unreacted starting material and / or by-product of any partial degradation, for example, hydrolysis, of the softening active ingredients in the final compositions. It is preferred that the level of free fatty acid be low, preferably less than about 10%, better still, less than about 5%, by weight of the softening active ingredient.
CONCENTRATED DISPERSION COMPOSITIONS The stable "dispersion" compositions which can be prepared using the novel compounds / compositions herein, are those which are described in the co-pending US patent application, Serial No. 08 / 461,207 filed thereon. June 5, 1995 by H. H. Wahl and co-inventors; said request being incorporated herein by reference.
B > THE SOLUBLE ORGANIC SYSTEM SOLUBLE BN WATER The dispersion compositions of the present invention optionally comprise about 5% to 30%, preferably about 8% to 25%, even better, about 10% to 20% by weight of the water-soluble organic solvent composition. The solvent is preferably mixed with the DEQA fabric softener to help provide low viscosity to facilitate processing, for example, pumping and / or mixing, even at ambient temperatures. Preferably the organic solvent is a water-soluble solvent, for example, ethanol, isopropanol, 1,2-propanediol, 1,3-propanediol, propylene carbonate, etc. The ability to create finished concentrated compositions, with conventional blending at ambient temperatures, for example, around 10 ° C to 40 ° C, preferably around 20 ° C to 35 ° C, with only low levels of water-soluble solvents, it is possible with the fabric softening compounds strongly unsaturated, described further back. This processing at ambient temperatures is very important when the dispersion compositions contain high levels of polyunsaturated softening actives.
C. THE PERFUME The premixes and / or finished compositions of the present invention may contain any perfume compatible with the softener. Preferred perfumes are written in US Patent 5,500,138, by Bacon and co-inventors, issued March 19, 1996; said patent being incorporated herein by reference. The perfume is optionally present at a level of about 0% to 10%, preferably about 0.1% to 5%, better still, about 0.2% to 3% by weight of the finished composition. It is an advantage of the use of this invention that the perfume can be added, preferably, in the premix to simplify the preparation of the final dispersion compositions, and to improve the deposition in the fabric of said perfume. The premix can be added to the water containing the necessary amount of acid, preferably a mineral acid, better still, HCl, to create the final composition discussed below.
! ---, THE STABILIZERS The stabilizers are highly convenient, and even essential, in the final dispersion compositions and, optionally, in the raw materials of the present invention.
The term "stabilizer", as used herein, includes antioxidants and reducing agents. These agents are present at a level of approximately 0% to 2%, preferably around 0.01% to 0.2%, better yet, about 0.035% to 0.1% for antioxidants and, more preferably, about 0.01% to 0. 2% for reducing agents, in the final composition. For the premix, the levels are adjusted depending on the concentrations of the softening active ingredient in the premix and in the final composition. This ensures good odor stability under long-term storage conditions. Antioxidants and stabilizers and reducing agent are especially critical for products without aroma or with little aroma (without perfume or with little perfume). Examples of antioxidants that can be added to the dispersion compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, obtainable from Eastman Chemical Products, Inc., under the ® ® brand names Tenox PG and Tenox Sl; a mixture of butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), propyl gallate and citric acid, obtainable from Eastman Chemical ® Products, Inc., under the trade name Tenox -6; butylated hydroxytoluene, obtainable from UOP Process Division, under the name ®. . . . commercial Sustane BHT; Tertiary butylhydroquinone, Eastman® Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox ® GT-1 / GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as HA; long-chain esters (8 to 22 carbon atoms) of γ-gallic acid, for example, dodecyl gallate; Irganox 1010, Irganox 1035, Irganox B 1171, Irganox 1425, Irganox 3114, Irganox ® ® 3125 and their mixtures; preferably Irganox 3124, Irganox 1425, ® ® Irganox 3114 and its mixtures, better yet, Irganox 3125, alone or mixed with citric acid and / or other chelating agents, such as ® isopropyl citrate, Dequest 2010, obtainable from Monsanto with the chemical name of 1-hydroxy-ethylidene 1, diphosphonic acid (etidronic acid) and Tiro, obtainable from Kodak under the chemical name of sodium salt of 4,5-d? hydrox? -m-benzenesulfon? co acid and DTPA, obtainable from Aldrich, with the chemical name of diethylenetriaminepentaacetic acid.
E. OPTIONAL INGREDIENTS ÍA- The brighteners The premix, and especially the final dispersion compositions herein may also optionally contain about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide an inhibition action of dye transfer. If used, the dispersion compositions herein will preferably comprise about 0.001% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners, useful in the present invention, are those that have the structural formula: wherein R ^ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation, such as sodium or potassium. When, in the above formula, R ^ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4 '-bis [(4-anilino-6- (N -2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-styrylisulfonic acid and the disodium salt. This particular polishing species is sold commercially under the trade name Tmopal -UNPA-GX ® by Ciba Geigy Corporation. Tinopal -UNPA-GX is the preferred hydrophilic optical brightener, useful in the dispersion compositions added in the rinse, of the present. When, in the previous formula, R] _ is aniline, R is? -2-hydroxyethyl-? -2-methylamino and M is a cation, such as sodium, the brightener is the disodium salt of 4,4 '-bis [(4-anilino-6- (? - 2-hydroxyethyl-β-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular brightener species is ® commercially sold under the trade name Tmopal 5BM-GX, by Ciba-Geigy Corporation. When, in the above formula, R? _ Is anilino, R is morphino and M is a cation, such as sodium, the brightener is the sodium salt of 4,4 '-bis [(4-anilino-6-morphino) acid -s-triazin-2-yl) amino] -2,2 '-stilbenedisulfonic acid. This particular species is sold commercially under the trade name Tinopal AMS-GX® by Ciba-Geigy Corporation.
The dispersion compositions of the present invention may optionally contain dispersibility aids, for example, those selected from the group consisting of cationic quaternary ammonium compounds with a single long chain alkyl; amine oxides with long single-chain alkyl and mixtures thereof, to assist in the formation of the final dispersion compositions. When said dispersibility aid is present, it is typically present at a total level of about 2% to 25%, preferably about 3% to 17%, better still, about 4% to 15% and even more preferably, about 5%. % to about 13% by weight of the composition. These materials can be added as part of the active softening raw material (I) or they can be added as a separate component. The total level of the dispersibility aid includes any amount that may be present as part of the component (I). (1) The monoalkyl cationic quaternary ammonium compound When the monoalkyl cationic quaternary ammonium compound is present, it is typically at a level of about 2% to 25%, preferably about 3% to 17%, better still, about 4% to 15% and still more preferable , from 5% to about 13% by weight of the composition, the total of the monoalkyl cationic quaternary ammonium compound being at least at an effective level. Said monoalkyl cationic quaternary ammonium compounds, useful in the present invention, are preferably the quaternary ammonium salts of the general formula: [R 4 N + (R 5) 3] X "wherein: R 4 is an alkyl or alkenyl group of 8 to 22 carbon atoms, preferably an alkyl or alkenyl group of 10 to 18 carbon atoms, better still, an alkyl or alkenyl group alkenyl of 10 to 14 carbon atoms or of 16 to 18 carbon atoms, each R 5 is an alkyl or substituted alkyl group of 1 to 6 carbon atoms (for example, hydroxyalkyl), preferably an alkyl group of 1 to 3 carbon atoms, for example the methyl group (most preferred) ethyl, propyl and the like, a benzyl group, hydrogen, a polyethoxylated chain with about 2 to 20 oxyethylene units, preferably about 2.5 to 13 oxyethylene units, better still , about 3 to 10 oxyethylene units, and their mixtures, - and X "is as defined hereinabove for formula (I). Especially preferred dispersing aids are monolauryltrimethylammonium chloride and monosebotrimethylammonium chloride obtainable from itco under the tradename Varisoft® 471 and the monooleyltrimethylammonium chloride obtainable from itco under the tradename Varisoft® 417. The R4 group can also be attached to cationic nitrogen atom through a group containing one or more ester, amide, ether, amine, etc. linking groups, which may be convenient for increasing the concentration capacity of component (I), etc. Said linking groups, preferably, are within about 1 to 3 carbon atoms of the nitrogen atom. The monoalkyl cationic quaternary ammonium compounds also include the alkylcoline esters of 8 to 22 carbon atoms in the alkyl. Preferred dispersibility aids, of this type, have the formula: R1C (O) -0-CH2CH2N + (R) 3X " wherein R1, R and X "are as previously defined Highly preferred dispersibility aids include cococolin ester of 12 to 14 carbon atoms and sebocholine ester of 16 to 18 carbon atoms. One long, biodegradable, suitable chain containing an ester linkage in the long chains are described in U.S. Patent No. 4,840,738, Hardy and Walley, issued June 20, 1989; This reference When the dispersibility aid comprises alkylcholine esters, preferably the dispersion compositions also contain a small amount, preferably about 2% to 5% by weight of the composition, of organic acid. The organic acids are described in European patent application No. 404,471, de Machín and co-inventors, published on December 27, 1990, supra, which is incorporated herein by this reference. Preferably, the organic acid is selected from the group consisting of glycolic acid, acetic acid, citric acid and mixtures thereof. The ethoxylated quaternary ammonium compounds which can serve as a dispersibility aid include ethylbis (polyethoxyethanol) alkylammonium ethiisulfate with 17 moles of ethylene oxide, obtainable under the tradename Vriquat® 66 from Sherex Chemical Company; polyethylene glycol (15) oleammonium chloride, obtainable under the tradename Ethoquad® 0/25 Akzo, - and polyethylene glycol (15) cocomonium chloride, obtainable under the trademark Ethoquad® C / 24 from Akzo. Although the main function of the dispersibility aid is to increase the dispersibility of the ester softener, preferably the dispersibility auxiliaries of the present invention also have certain softening properties to enhance the softening performance of the composition. Therefore, preferably, the dispersion compositions of the present invention are essentially free of ethoxylated, non-nitrogenous non-ionic dispersing aids, which will decrease the overall softening performance of the dispersion compositions. Also, quaternary compounds having only a single long alkyl chain can protect the cationic softener against its interaction with anionic surfactants and / or builders that are carried over into the rinse from the wash solution. 2. The amine oxides Suitable amine oxides include those having an alkyl or hydroxyalkyl portion of about 8 to 22 carbon atoms, preferably about 10 to 18 carbon atoms, better still, about 8 to 14 carbon atoms, and two alkyl portions selected from the group consisting of alkyl groups and hydroxyalkyl groups with about 1 to 3 carbon atoms. Examples include: dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide and fatty alkyl oxide. -dimethylamine.
(C) THE MUGRE APPROVING AGENT In the present invention, an optional filler may be added, in particular to the final dispersion compositions. The addition of the soil release agent can occur in combination with the premix, in combination with the acid / water seat, before or after the electrolyte addition, or after the final composition is made. The final softening composition, prepared by the process of the present invention, may contain from 0% to 10%, preferably from 0.2% to 5%, of a sludge-releasing agent. The concentration in the premix is adjusted to give the desired final concentration. Preferably, said filtering agent is a polymer. The polymeric soil release agents useful in the present invention include copolymer blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like. A preferred sludge-removing agent is a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers consist of repeating units of ethylene terephthalate and polyethylene oxide terephthalate, at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units from 25:75 to about 35:65; said ethylene oxide terephthalate contains polyethylene oxide blocks having approximate molecular weights of from 300 to 2,000. The molecular weight of this polymeric filtering agent is about 5,000 to 55,000. Another preferred polymeric slurry agent is a crystallizable polyester with repeating units of ethylene terephthalate units containing about 10% to 15% by weight of ethylene terephthalate units with about 10% to 50% by weight of polyoxyethylene terephthalate units. , derived from a polyoxyethylene glycol of average molecular weight of approximately 300 to 6,000; and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymer compound is between 2: 1 and 6: 1. Examples of this polymer include the commercially available materials Zelcon 4780® (from DuPont) and Milease T® (from Id). The most preferred soil release agents are polymers of the generic formula: 0 0 0 0 X - (0CH2CH2) p (0 - C I - R 144-C II - 0R 1l5) u (0-C II-R 144-0C II-0) (CH2CH20-) n-X wherein each X can be a suitable crown group, with each X typically being selected from the group consisting of H and alkyl or acyl groups containing about 1 to 4 carbon atoms. P is selected for solubility in water and, in general, is about 6 to 113, preferably about 20 to 50. The u value is critical for the formulation in a liquid composition having a relatively high ionic strength. There must be very little material in which u is greater than 10. Additionally, there must be at least 20%, preferably at least 40%, of material in which u varies from 3 to 5, approximately. The R14 portions are essentially 1,4-phenylene portions. As used herein, the term "R14 portions are essentially 1,4-phenylene portions" refers to the compound in which portions R14 consist entirely of portions 1, 4-phenylene or are partially substituted with other arylene or alkarylene portions, alkylene portions, alkenylene portions or mixtures thereof. The arylene and alkarylene portions that may be partially substituted by 1,4-phenylene include: 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4, 4-biphenylene and its mixtures. The alkylene and alkenylene portions that may be partially substituted include: 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1, 4-cyclohexylene and its mixtures. For the portions R, the degree of partial substitution with different portions of 1,4-phenylene should be such that the soil-loosening properties of the compound are not adversely affected, to any great extent. In general, the degree of partial substitution that can be tolerated will depend on the length of the skeleton of the compound; that is, the longer skeletons may have higher partial substitution for the 1, 4-phenylene portions. Usually, the compounds in which R14 comprises about 50% to 100% of 1,4-phenylene portions (from 0% to 50% of different portions of 1,4-phenylene) have adequate soil loosening activity. For example, polyesters made in accordance with the present invention, with a 40:60 molar ratio of isophthalic acid (1,3-phenylene) to terephthalic acid (1,4-phenylene) have suitable soil loosening activity. However, since most of the polyesters used in the formation of the fibers comprise ethylene terephthalate units, it is usually convenient to minimize the degree of partial substitution with different portions of 1,4-phenylene, for better water-loosening activity. dirt. Preferably, the R14 portions consist entirely of (i.e., comprise 100%) of 1,4-phenylene portions, ie, each R14 portion is 1,4-phenylene. For the R 5 portions, suitable ethylene or substituted ethylene portions include: ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene and mixtures thereof. Preferably the portions R15 are essentially ethylene portions, 1,2-propylene moieties or mixtures thereof. The inclusion in a greater percentage of the ethylene portions tends to improve the soil loosening activity of the compounds. Surprisingly, the inclusion of a higher percentage of 1,2-propylene portions tends to improve the water solubility of the compounds. Accordingly, the use of 1,2-propylene portions or a similar branched equivalent is convenient for the incorporation of any substantial part of the grime-sifting component into liquid, fabric softening dispersion compositions. Preferably, about 75% to about 100% are 1,2-propylene portions. The value for each p is at least about 6, and preferably at least about 10. The value for each n usually varies from about 12 to about 113. Typically, the value for each p is on the scale Approximately 12 to 43. A more complete description of the grubbing agents is contained in U.S. Patent Nos. 4,661,267 to Decker, Konig, Straathof and Gosselink, issued April 28, 1987; 4,711,730, Gosselink and Diehl, issued December 8, 1987; 4,749,596 to Evans, Huntington, Stewart, wolf and zimmerer, issued June 7, 1988; 4,818,569, by Trinh, Gosselink and Rattinger, issued April 4, 1989; 4,877,896, by Maldonado, Trinh and Gosselink, issued on October 31, 1989; 4,956,447 of Gosselink and co-inventors, issued on September 11, 1990 and 4,976,879, of Maldonado, Trinh and Gosselink, issued on December 11, 1990; all these patents are incorporated herein by reference. These soil release agents can also act as foam dispersants.
ID-. BL DISPERS TE PE FOAM In the present invention, the premix can be combined with an optional foam dispersant, different from the gritting agent, and can be heated to a temperature equal to or greater than the melting point (s) of the components. Foam dispersants are desirable components in the final dispersion compositions herein. Preferred foam dispersants are formed by strongly ethoxylating the hydrophobic materials. The hydrophobic material can be a fatty alcohol, a fatty acid, a fatty amine, a fatty acid amide, an amine oxide, a quaternary ammonium compound, or the hydrophobic portions used to form soil release polymers. Preferred foam dispersants are strongly ethoxylated, for example, more than about 17, preferably more than about 25, better still, more than about 40 moles of ethylene oxide per molecule on average, with the polyethylene oxide moiety being about 76% to about 97%, preferably about 81% to 94% of the total molecular weight.
The level of foam dispersant is sufficient to keep the foam at an acceptable level, preferably not noticeable to the consumer, under the conditions of use, but not sufficient to adversely affect the smoothing. For certain purposes it is convenient that the foam is non-existent. Depending on the amount of anionic or non-ionic detergent, etc., used in the wash cycle of a typical laundry process, the efficiency of the rinse steps before the introduction of the dispersion compositions of the present and the the hardness of the water, the amount of anionic or nonionic detergent surfactant and builder (especially the phosphates and zeolites) trapped in the (wash) fabric will vary. Normally, the minimum amount of foam dispersant should be used to avoid adversely affecting the softening properties. Typically, the foam dispersion requires at least about 2%, preferably at least about 4% (at least 6% and preferably at least 10% for maximum foam avoidance) based on the level of active ingredient softener. However, at approximate levels of 10% (relative to the softening material) or more, there is a risk of losing the softening efficacy of the product, especially when the fabrics contain high proportions of nonionic surfactant, which has been absorbed during the washing operation. . The preferred foam dispersants are Brij 700®, Varonic U-250®, Genapol T-500®, Genapol T-800®, Plurafac A-79®, Plurafac A-79® and Neodol 25-50®. i ---) THE BACTERICIDES Examples of bactericides used in the premixes and / or in the final dispersion compositions of this invention include: glutaraldehyde, formaldehyde, 2-bromo-2-nitropropane-1,3-diol, sold by Inolex Chemicals, located in Philadelphia, Pennsylvania , USA, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, sold by Rohm and Haas Company, under the commercial name Kathon CG / ICP®. Typical levels of bactericides used in the dispersion compositions herein are about 1 to 1,000 ppm by weight of the agent.
THE LOSSING AGENTS The final dispersion compositions and methods herein may optionally employ one or more copper and / or nickel chelating agents ("chelators"). Said water soluble chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, aromatic chelating agents, polyfunctionally substituted and their mixtures, - all as defined below. The whiteness and / or the brightness of the fabrics are substantially improved or restored by said chelating agents and the stability of the materials in the dispersion compositions is improved.
Aminocarboxylates useful as chelating agents herein include: ethylenediaminetetraacetates (EDTA), N-hydroxyethylenediamine-triacetates, nitrilotriacetates (NTA), ethylenediaminetetrapropionates, ethylenediamine-N, N'-diglutamates, 2-hydroxypropylene-diamino-N, N ' -disuccinates, triethylenetetraaminohexaacetates, diethylenetriaminepentaacetates (DETPA), and ethanoldiglicines, which include their water soluble salts, such as the alkali metal, ammonium and substituted ammonium salts, and mixtures thereof. The aminophosphonates are also suitable for use as chelating agents in the dispersion compositions of the invention, when at least low levels of total phosphorus are permitted in the dispersion detergent compositions, and include: ethylenediaminetetracis (methylenephosphonates), diethylenetriamine-N, N, N ', N ", N" -pentacis (methanphosphonate) (DETMP) and 1-hydroxyethane-1-diphosphonate (HEDP). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Chelating agents are typically used in the rinse process of the present at approximate levels of 2 ppm to 25 ppm, for periods of 1 minute until soaking for several hours. The preferred EDDS chelator used herein (also known as N, N'-ethylenediamine disuccinate) is the material described in U.S. Patent 4,704,233, cited hereinabove, and has the formula (shown in the free acid form): As described in the patent, EDDS can be prepared using maleic anhydride and ethylenediamine. The preferred, biodegradable [S, S] isomer of EDDS can be prepared by reacting L-aspartic acid with 1,2-dibromoethane. EDDS has advantages over other chelators, since it is effective for chelating copper and nickel cations, is available in a biodegradable form and does not contain phosphorus. The EDDS employed herein as a chelator is typically in the form of its salt, wherein one or more of the four acid hydrogens is (are) replaced by a water-soluble M cation, such as sodium, potassium, ammonium, triethanolammonium. and similar. As noted above, the EDDS chelator is also typically used in the rinse procedure herein at approximate levels of 2 ppm to 25 ppm, for periods of 1 minute until soaking for several hours. At certain pH values, the EDDS is preferably used in combination with zinc cations. As you can see from the above, you can use a wide variety of chelators here. Actually, simple polycarboxylates, such as citrate, oxydisuccinate and the like, may also be used, although such chelators are not as effective as the aminocarboxylates and phosphonates, on a weight basis. Consequently, the levels of use can be adjusted to take into account the degrees of difference in the effectiveness of ironing. Chelators of the present will preferably have a stability constant (of the fully ionized chelator) for the copper ions of at least about 5, preferably at least about 7. Typically, the chelating agents will comprise about 0.5% to 10% , better still, from 0.75% to 5%, by weight of the dispersion compositions herein. Preferred chelators include DETMP, DETPA, NTA, EDDS and their mixtures.
------ OPTIONAL VISCOSIDAP / DISPERSABILITY MODIFIERS The relatively concentrated, final dispersion compositions containing the unsaturated diester quaternary ammonium compounds herein can be prepared so that they are stable without the addition of concentration aids. However, the dispersion compositions of the present invention may require organic and / or inorganic concentration aids, to reach even higher concentrations and / or to satisfy higher stability standards, depending on the other ingredients. These concentration aids which typically can be viscosity modifiers may be necessary or preferred to ensure stability under extreme conditions, when particular levels of active softener are used. The surfactant concentration aids are typically selected from the group consisting of: (1) long chain single cationic alkyl surfactants, - (2) nonionic surfactants, - (3) amine oxides, - (4) ) fatty acids and (5) mixtures of them. These auxiliaries are described in the pending Procter & amp; Gamble Serial No. 08 / 461,207, filed on June 5, 1995, Wahl and co-inventors, specifically on page 14, line 12 to page 20, line 12, which is incorporated herein by this reference.
AM1 OTHER OPTIONAL INGREDIENTS The final dispersion compositions of the present invention may include optional components conventionally used in dispersion compositions for the treatment of textiles, for example: colorants, preservatives, surfactants, anti-shrinkage agents, fabric binding agents, scavenging agents of stains, germicides, fungicides, antioxidants, such as butylated hydroxytoluene, anti-corrosion agents and the like. Particularly preferred ingredients include water-soluble calcium and / or magnesium compounds, which provide additional stability. Chloride salts are preferred, but acetate, nitrate, etc. salts can also be used. The level of the calcium and / or magnesium salts is from 0% to 2%, preferably around 0.05% to 0.5%, better still, around 0.1% to 0.25%. These materials are conveniently added to the water and / or the acid (water seat) used to prepare the final dispersion compositions to help adjust the final viscosity. The present invention also includes other compatible ingredients including those described in the pending applications Serial No. 08 / 372,068, filed on January 12, 1995, by Rusche and co-inventors; 08 / 372,490, filed January 12, 1995, Shaw and co-inventors, - and 08 / 277,558, filed July 19, 1994, Hartman and co-inventors, all incorporated herein by this reference. The invention is exemplified by the following non-limiting examples, in all of which the numerical values are approximations consistent with normal experience. The compositions with preheated softening active ingredient can be prepared by adding it to the "water seat" comprising the water and minor ingredients, but it is best done at room temperature, especially after premixing the active ingredient and the perfume.
PREPARATION OF ACTIVE INGREDIENTS FABRIC SOFTENERS. BIODEGRADABLES A preferred source of triglycerides, which can be used to prepare the fabric softening compositions herein is canola oil. Canola oil is a mixture of triglycerides having an appropriate chain length distribution and the degree of unsaturation of the respective acyl groups. Canola oil is a suitable starting material according to the process of the present invention, for several reasons. In particular, its natural distribution of the chain lengths of the respective acyl groups has a remarkably high proportion of acyl groups containing 18 carbon atoms, thus avoiding the additional cost that is incurred when using other commercial sources of fatty acids of 18 carbon atoms, as starting materials. The starting material triglyceride can be hydrogenated, if desired, to convert the diunsaturated and triunsaturated acyl groups, particularly those containing 18 carbon atoms, to their monounsaturated counterparts. It is usually convenient that the hydrogenation of the monounsaturated acyl groups is the minimum and even that it is completely avoided. Saturated acyl groups can be obtained from normally saturated sources and mixed with unsaturated acyl groups. In some useful mixtures of acyl groups, no more than about 10% of the acyl groups of 18 carbon atoms, unsaturated, are hydrogenated to their saturated counterparts. For some products, preferably the hydrogenation of the acyl groups of 18 carbon atoms, diunsaturated and triunsaturated is the maximum, consistent with the minimum formation of saturated groups of 18 carbon atoms. The tri-unsaturated acyl groups, for example, can be completely hydrogenated, without obtaining complete hydrogenation of the di-unsaturated acyl groups. The hydrogenation of the starting material triglyceride which maximizes the monounsaturated acyl groups can be easily obtained by maintaining an appropriate balance of the hydrogenation reaction conditions. The process variables in the hydrogenation of the triglycerides and the effects of altering those variables, are generally quite familiar to an ordinary expert in the field. In general, the hydrogenation of the triglyceride starting material can be carried out at a temperature which varies (broadly stated) between about 170 ° C and about 205 ° C and, better yet, within a somewhat smaller scale of about 185 ° C and around 195 ° C. Another significant process variable is the hydrogen pressure inside the hydrogenation reactor. In general, this pressure should be maintained within a scale (broadly stated) of around 0.14 to about 1.40 kg / cm2 gauge and, better yet, between about 0.351 and 1.05 kg / cm2 gauge. Within these parameter scales, hydrogenation can be carried out with particular observation of the effects of these parameters. The lower hydrogen pressures in the reactor allow a greater degree of control of the reaction, in particular as regards its selectivity. By "selectivity" is meant the hydrogenation of the diunsaturated and triunsaturated acyl groups without excessive hydrogenation of the monounsaturated acyl groups. On the other hand, higher hydrogen pressures produce less selectivity. Selectivity may be desirable in certain cases. The higher hydrogenation temperatures are associated with faster hydrogenation rates and with greater selectivity of hydrogenation. Conversely, lower hydrogenation temperatures are associated with less selectivity (ie, increased hydrogenation of the monounsaturated groups) and, in particular, with slower rates of hydrogenation, in general. These considerations are also balanced with consideration to the stereochemistry. More specifically, the presence of unsaturation in the acyl groups can lead to the formation of different stereoisomers in the acyl groups, by hydrogenation. The two possible stereoisomeric configurations for the unsaturated fatty acyl groups are known as the "cis" and "trans" forms. The presence of the cis form is preferred, since it is associated with a lower melting point of the eventual product and, thus, with greater fluidity. Thus, another reason why canola oil is a particularly preferred triglyceride starting product, is that, as a material occurring in nature, the acyl groups present in its triglyceride exhibit only the cis form. In the hydrogenation, the higher hydrogen pressures are also associated with a lower tendency of the acyl group to undergo a change in configuration from the cis form to the trans form. Also the higher hydrogenation temperatures, although favorable for some reasons, are also associated with the greater conversion of cis unsaturation to the trans form. Products exhibiting satisfactory properties can be obtained by appropriate control of the hydrogenation conditions, in order to produce both selectivity and control of the stereochemical configurations of the product. Hydrogenation is carried out in the presence of a suitable hydrogenation catalyst. These catalysts are well known and are obtained commercially. In general they comprise nickel, palladium, ruthenium or platinum, typically on a catalyst support. A suitable catalyst is a nickel-based catalyst, such as that sold by Engelhard under the trade designation "N-545". In one variation, the hydrogenation is carried out to a final point, in which the hydrogenation of the diunsaturation and the tri-saturation in the triglyceride product is the maximum, while the formation of saturated acyl groups is the minimum. The progress of the hydrogenation reaction towards the end point can be easily monitored by periodically measuring the iodine value of the reaction mass. As the hydrogenation progresses, the iodine value decreases. For example, the hydrogenation reaction can be discontinued when the iodine value reaches about 95. Other requirements for hydrogenation reactions are well known, such as reactor types, cooling media to maintain the desired temperature, provision of media for agitation, effective to provide adequate contact between triglyceride and hydrogen, and catalyst, etc. The triglyceride containing the desired acyl groups is typically hydrolyzed to obtain the desired fatty acyl groups, such as, for example, the corresponding fatty acids. That is, the after ester ligatures in the triglyceride are broken so that the hydrogenated combination of the acyl groups is converted to mixtures of fatty acids having the same chain length distribution as in the acyl groups, and having the distribution of saturation and unsaturation provided by the hydrogenation reaction. However, other approaches include using transesterification to create, for example, methyl esters, which can then be used to esterify the alkanolamine, as described below. The hydrolysis can be carried out under any of the suitable conditions known in the art for the hydrolysis of triglycerides to their fatty acid constituents. In general, the triglyceride is reacted with steam at a high temperature in a reactor, in which the fatty acids are released from the glycerin, after which the steam condenses to form an aqueous solution of glycerin, and this solution is eliminated . The fatty acid mixture obtained in the hydrolysis step is then used to esterify, for example, one or more amines of the formula RN (CH CH 2 OH) 2, wherein R is as defined above and, preferably, It is methyl. Alternatively, the desired esterification can be obtained by transesterifying with the corresponding fatty acyl ester, such as the methyl ester. The esterification can be carried out under conventional esterification conditions, providing an acid catalyst and providing extraction of the by-produced condensation water. Preferably a small amount, generally up to about 1.0% by weight of the reactant (ie, the acids and the amine), of hypophosphorous acid (HPPA) can be added to the esterification reaction mixture. It is believed that HPPA catalyses the reaction and maintains, or even improves, the color of the product obtained in that reaction. In one embodiment of this invention, the esterification is allowed to proceed completely, so that all the amine present is diesterified with the fatty acids produced in the previous hydrolysis step. However, it is sometimes convenient to produce a smaller amount of the corresponding monoester, as discussed further back. The mixture of diesters or the mixture of diester and monoester components is quaternized, as the case may be. Quaternization is carried out under conditions and with reagents that are generally familiar to those who have experience in this field. The quaternizing agent has the formula RX, wherein R is preferably methyl, benzyl or ethyl and X is the anion that was defined above. Preferably RX is methyl chloride, benzyl chloride, dimethyl sulfate or diethyl sulfate. This cauterization step produces a mixture of biodegradable, fabric softening active ingredients, as described hereinabove. It is highly desirable that the compounds used here be relatively free of undesirable impurities. Accordingly, it is convenient to process the fatty acid sources according to some known manner, to remove said impurities, for example, by processing under atmospheres that are low in oxygen, separating the undesirable materials by filtration, adsorption, etc., either before and / or after chemical modification, by controlled hydrogenation and / or oxygenation, etc. However, the purity of the materials is not part of the present invention, which is equally applicable to less pure materials, the choice between purity and cost being adjusted, always in light of the wishes and needs of the consumer. The synthesis of the biodegradable fabric softening active ingredient mixtures of the present invention is further illustrated in the following synthesis examples. These synthesis examples are given solely for illustrative purposes.
About 1.00 g of canola oil and about 6.5 g of a commercial nickel hydrogenation catalyst (Engelhard, "N-545") corresponding to approximately 0.13% by weight of Ni, are placed in a hydrogenation reactor that It is equipped with agitator. The reactor is sealed and evacuated. The contents are heated to about 170 ° C and hydrogen is fed to the reactor. Stirring is maintained at 450 rpm throughout the reaction. After about 10 minutes, the temperature in the reactor is around 191 ° C and the hydrogen pressure is 0.773 kg / cm2 gauge. The temperature is maintained at around 190 ° C. After about 127 minutes since the hydrogen feed began, the hydrogen pressure is around 0.703 kg / cm2 gauge. A sample of the reaction mass is extracted and found to have an approximate iodine value of 78.0 and a cis: trans ratio of about 1.098. After another 20 minutes at about 190 ° C the hydrogen pressure is around 0.688 kg / cm2 gauge. The hydrogen feed is interrupted and the contents are cooled in the reactor, with stirring. The final reaction product has an approximate iodine value of 74.5 and a cis: trans ratio of about 1.35. The product that is formed in the reactor is removed and filtered. It has a turbidity point of approximately 22.2 ° C. It is determined that the chain length distributions of the acyl substituents in the sample taken at about 127 minutes and the final product are as shown in Table 1, in which "sat" means saturated and "mono" and "di" "signify, respectively, monounsaturated and diunsaturated.
TABLE 1 Approximate (molar) percentage Chain length Sample at 127 min Product C14-sat 0.1 0.1 C16-sat 4.7 4.6 C16-mono. 0.4 0.4 C18-sat 8.9 13.25 C18-mono 77.0 73.8 C18-di 4.5 3.1 C20-sat 0.7 0.75 C20-mono 2.1 2.0 Other 1.6 2.0 EXAMPLE B COMPOUND SYNTHESIS About 1,300 g of canola oil and about 5.2 g of Engelhard nickel hydrogenation catalyst "N-545" are placed in a hydrogenation reactor equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 175 ° C and hydrogen is fed to the reactor. Stirring is maintained at around 450 rpm throughout the course of the reaction. After about 5 minutes the temperature in the reactor is around 190 ° C and the hydrogen pressure is around 0.492 kg / cm2 gauge. The temperature is maintained at around 190 ° C. After about 125 minutes from the start of the hydrogen feed, the hydrogen pressure is around 0.492 kg / cm2 gauge. A sample is drawn from the reaction mass and found to have an iodine value of 85.4. After another 20 minutes or so at around 190 ° C the hydrogen pressure is around 0.421 kg / cm2 gauge. The hydrogen supply is interrupted and the contents of the reactor are cooled while being stirred. The final reaction product has an iodine value of about 80.0. The product that is formed in the reactor is removed and filtered. It has a turbidity point of approximately 18.6 ° C.
EXAMPLE C SYNTHESIS About 1,300 g of canola oil and about 2.9 g of nickel hydrogenation catalyst "N-545" from Engelhard are placed in a hydrogenation reactor that is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 180 ° C and hydrogen is fed to the reactor. Stirring is maintained at around 450 rpm throughout the course of the reaction. After about 5 minutes the temperature in the reactor is around 192 ° C and the hydrogen pressure is around 0.703 kg / cm2 gauge. The temperature is maintained at around 190 ± 3 ° C. After about 105 minutes from the start of the hydrogen feed, the hydrogen pressure is around 0.703 kg / cm2 gauge. A sample is extracted from the reaction mass and found to have an iodine value of 85.5. After another 20 minutes at about 190 ° C, the hydrogen pressure is around 0.703 kg / cm2 gauge. The hydrogen supply is interrupted and the contents of the reactor are cooled while being stirred. The final reaction product has an iodine value of about 82.4. The product that is formed in the reactor is removed and filtered. It has a turbidity point of approximately 17.2 ° C.
EXAMPLE D COMPOUND SYNTHESIS About 1,300 g of canola oil and about 1.4 g of nickel hydrogenation catalyst "N-545" from Engelhard are placed in a hydrogenation reactor that is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 180 ° C, hydrogen is fed to the reactor. After 5 minutes the temperature in the reactor is around 191 ° C and the hydrogen pressure is around 0.703 kg / cm2 gauge. The temperature is maintained at around 190 ± 3 ° C. After about 100 minutes from the start of the hydrogen feed, the hydrogen pressure is about 0.703 kg / cm2 gauge. A sample is drawn from the reaction mass and found to have an approximate iodine value of 95.4. After another 20 minutes at about 190 ° C, the hydrogen pressure is around 0.703 kg / cm2. The hydrogen feed is interrupted and the contents of the reactor are cooled with stirring. The final product of the reaction had an iodine value of about 2.3. The product formed in the reactor is removed and filtered. It has a turbidity point of approximately 34 ° C.
EXAMPLE E COMPOUND SYNTHESIS About 1,300 g of canola oil and about 1.3 g of "N-545" nickel hydrogenation catalyst from Engelhard are placed in a hydrogenation reactor which is equipped with stirrer. The reactor is sealed and evacuated. The contents are heated to about 190 ° C and hydrogen is fed to the reactor at an approximate hydrogen pressure of 0.351 kg / cm2 gauge. After about 3 hours from the start of the hydrogen feed, a sample is withdrawn from the reaction mass and found to have an iodine value of about 98. The hydrogenation is stopped, another 0.7 g thereof is added. catalyst and the reaction conditions are re-established at around 190 ° C for another hour. The hydrogen feed is then interrupted and the contents of the reactor cooled, while being stirred. The final reaction product had an approximate iodine value of 89.9. The product that is formed in the reactor is removed and filtered. It has a cloud point of around 16.0 ° C.
EXAMPLE F COMPOUND SYNTHESIS About 1,300 g of canola oil and about 2.0 g of nickel hydrogenation catalyst "N-545" from Engelhard are placed in a hydrogenation reactor which is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 190 ° C and hydrogen is fed to the reactor at a hydrogen pressure of about 0.351 kg / cm 2 gauge. Agitation is maintained at about 420 rpm during the entire course of the hydrogen feed reaction. After about 130 minutes from the start of the hydrogen feed, the hydrogen feed is interrupted and the contents of the reactor are cooled while being stirred. The final reaction product had an iodine value of about 96.4. The product that is formed in the reactor is removed and filtered. It has a cloud point of approximately 11.2 ° C.
A mixture of about three times is hydrolysed 1,200 g of the hydrogenated oil of Synthesis Example F and about 200 g of the hydrogenated oil of Synthesis Example A, with steam at about 250 ° C, at about 42.18 kg / cm 2 gauge for about 2.5 hours, at a rate of steam: oil of about 1.2 (in weight). An aqueous solution containing the glycerin that had come off is removed. The resulting mixture of fatty acids is vacuum distilled for a total of about 150 minutes, in which the temperature of the vessel gradually rose from about 200 ° C to about 238 ° C, and the temperature of the vessel gradually rose. column from 175 ° C to 197 ° C, approximately. The vacuum is maintained around 0.3-0.6 mm.
The fatty acids produced in the vacuum distillation have an approximate iodine value of 99.1, an amine value (VA) of about 197.6 and an approximate saponification value (SAP) of 198.6.
EXAMPLE H OF COMPOSITE DB SYNTHESIS About 800 g of mixture of fatty acids obtained from canola oil is placed by the preceding procedures; about 194.4 g of MDEA (methyldiethanolamine), about 2 g of BHT (butylated hydroxytoluene) and about 1 g of an approximately 50% by weight aqueous solution of HPPA, in a vessel, at the bottom of a distillation column. A flow of nitrogen is established through the column. The vessel is heated and distillation started at a vessel temperature of about 150 ° C and a column temperature of about 102 ° C. The temperature of the mixture was raised to about 193 ° C in a first hour and then gradually raised to about 202 ° C for the next 4 hours, more or less. The column temperature was raised to about 107 ° C in the first hour and then gradually declined to around 62 ° C for the next 4 hours, more or less. The product was then cooled in the vessel, recovered and analyzed. The distillate contained about 3% by weight of MDEA, about 51 g of water and exhibited a total amine value (VTA) of about 0.5. The product remaining in the container has a total amine value (VTA) of about 93.3.
EXAMPLE I COMPONENT SYNTHESIS It is combined in a sealed reactor about 900 g of the product of the synthesis example H, about 158 g of ethanol, about 0.3 g of ADPA, 1-hydroxyethane-1, 1-difusphonic acid (a chelator, for color) around of 0.15 g of antifoam, a sufficient amount of methyl chloride to establish an initial pressure of about 3022 kg / crrr gauge. After about 7 minutes the temperature is around 106 ° C and the pressure around 5.90 kg / cm2 gauge. Then the contents are maintained at around 105 ± 1 ° C for about 3-5 hours, while maintaining the pressure at around 4,007 + 0,140 kg / cm2 gauge, by the addition of methyl chloride. Then the reactor is opened and the contents are cooled to around 95 ° C. A total of about 110 g of methyl chloride is used. The product is then removed and divided at around 65 ° C in a rotary evaporator. The product has a diester content of approximately 75.9% and an approximate monoester content of about 11.4%.
EXAMPLES 1 TO 4 ingredients Ex. l Ex. 2 Ex. 3 Ex. 4% by weight% by weight% by weight% by weight DEQA1 (85% active in 17.7 23.5 30.6 30.6 ethanol perfume 0.8 1 1.35 - Tenox 6 0.02 0.03 0.04 0.04 CaCl2 (solution al.2 1.5 2 2 25% HCl IN 0.17 0.23 0.30 0.30 Distilled water rest rest rest rest EXAMPLES 1 TO 3 - PROCEDURE The compositions of Examples 1 to 3 are prepared at room temperature, by the following procedure: 1. The water seat containing HCl 2 is prepared. Separately, the perfume and the antioxidant Tenox are mixed with the active ingredient diester softener. 3. The diester active ingredient mixture is added to the water seat, with mixing. 4. About 10-20% of the CaCl2 solution is added approximately to half of the addition of the diester. 5. The remainder of the CaCl 2 solution is added after the diester addition is complete, with mixing.
Ingredients Ejem. 1 Axis 2 Axis 3 Axis 4% by weight% by weight% by weight% by weight DEQA5 (85% active 17.7 23.5 30.6 30.6 in ethanol) Perfume 0.8 1 1.35 - Tenox 6 0.02 0.03 0.04 0.04 CaCl2 (solution al.2 1.5 2 2 25%) HCl IN 0.17 0.23 0.30 0.30 Distilled water rest rest rest rest EXAMPLES 4 TO 6 - PROCEDURE The compositions of Examples 5 to 8 are prepared in a manner similar to those of Examples 1 to 4, except that DEQA5 is used in place of DEQA1. The compositions of Examples 1 to 8 have good viscosity. They are frozen when they are in a room at room temperature for three days, at a temperature of -18 ° C. After thawing at room temperature, the compositions are recovered as a fluid and have good viscosity.
COMPARATIVE EXAMPLES 9 TO 12 The compositions of Comparative Examples 9 to 12 are prepared in a manner similar to those of Examples 1 to 4, except that (a) DEQA11 (prepared from a slightly hydrogenated tallow fatty acid) is used instead of DEQA1 , - (b) it is necessary to heat the softening active ingredient to melt it at around 75 ° C, before adding it to the water seat, also preheated to around 75 ° C, - (c) it is necessary to provide about 50% more of CaCl2 to obtain good product viscosity, - and (d), the perfume is finally added to the final chilled composition, to avoid degradation of the perfume. The compositions of Examples 9 to 12 have good viscosity when cooled after preparation at room temperature. However, after they were frozen, they were placed in a room at constant temperature, for about 3 days, at a temperature of about -18 ° C and then thawed at room temperature; these compositions do not recover and remain thick or have a lumpy consistency.
EXAMPLES 13 AND 14 Ingredients Example 13 Example 14% by weight% by weight DEQA8 (85% active e? S0.6 - ethanol) DEQA9 (85% active ei-- 30.6 ethanol) Perfume 1.35 1.35 Tenox 6 0.04 0.04 CaCl2 (solution a22 2 25% ) HCl IN 0.30 0.30 Distilled water rest rest EXAMPLES 13 AND 14 The compositions of Examples 13 and 14 are prepared in a manner similar to that of Example 3, except that DEQA8 and DEQA9 are used in place of DEQA1.
EXAMPLES 15 AND 16 Ingredients Example 15 Example 16% by weight% by weight DEQA10 (85% active er20.8 ethanol) DEQA11 (85% active in - 20.8 ethanol) Perfume 1.35 1.35 Tenox 6 0.04 0.04 CaCl2 (solution aB 2 25%) HCl IN 0.30 0.30 Distilled water rest rest

Claims (9)

NOVELTY OF THE INVENTION CLAIMS
1. - Liquid, aqueous, concentrated fabric softening composition, characterized in that it comprises: (A) about 15% to 50% of biodegradable softening active ingredient, selected from the group consisting of (1): [(R) 4-m-N (+) - [(CH2) n-Y-R1] m] ^ | X (-) (1) wherein each R substituent is a short chain alkyl or hydroxyalkyl group, of 1 to 6 carbon atoms, benzyl or their mixtures, - each m is 2 or 3, each n is from 1 to 4, approximately; each Y is -0- (0) C- or -C (0) -0-, - each R is a hydrocarbyl or substituted hydrocarbyl group; the sum of the carbons in each R1 plus one when Y is -0- (0) C- is from 12 to 22 carbon atoms, - the average iodine value of the original fatty acid of group R is from 60 to 140, approximately , and where the opposite ion, X ~ is any anion compatible with the softener; (2) .- Softener that has the formula: (2) wherein each Y, R, R1 and X * 'have the same meanings as before, - and (3) their mixtures, - (B) optionally, about 0% to 10% perfume; (C) optionally around 0% to 2% stabilizer; and (D) the balance being a liquid carrier comprising water and an optional low molecular weight alcohol, the composition having a viscosity of less than about 1,000 cps after freezing and thawing.
2. - The composition in accordance with the claim 1, further characterized in that it comprises about 16% to 35% of softening active ingredient, selected from the group consisting of: (1) softening active ingredient having the formula: [(R) 4-m-N (+) - [(CH2) n-Y-R1] m] ^ | (-) (1) wherein each substituent R is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or mixtures thereof, - each m is 2 or 3; each n is 1 to about 4, - each Y is -0- (0) C -, - each R1 is a long chain hydrocarbyl or substituted hydrocarbyl substituent, of 13 to 19 carbon atoms, - the iodine value being (VY) of the original fatty acid of this group R1 about 70 to 130; and wherein the opposite ion, X ~ is chloride, - (2) softening active ingredient having the formula: wherein each Y, R, R1 and X ^ ~ 'have the same meanings as before, - and (3) their mixtures.
3. The composition according to claim 2, further characterized in that the softening active ingredient has the formula: [(R) 4-m-N (+) - [(CH2) n-Y-R1] m] ^] X (-) (1) wherein each substituent R is an alkyl or hydroxy alkyl group of 1 to 3 carbon atoms, benzyl or mixtures thereof, - each m is 2, - each n is from 1 to about 4; and the VY of the original fatty acid of the group R1 is around 80 to 115.
4. - The composition in accordance with the claim 1, further characterized in that the weight ratio of cis / trans isomers in the active ingredient is about 1: 1 to 50: 1.
5. - The composition in accordance with the claim 4, further characterized in that the weight ratio of cis / trans isomers in the active ingredient is about 3: 1 to about 30: 1. 6.- The composition in accordance with the claim 1, further characterized in that the softening active ingredient comprises up to about 20% monoester compound, wherein m is 2 and a YR1 is H or -C (0) OH. 7. - The process for forming the composition of claim 1, characterized in that the softening active ingredient is mixed with water at room temperature. 8. The process according to claim 7, further characterized in that the perfume is combined with the softening active ingredient before the softening active ingredient is added to the water. 9. The process for treating fabrics with the composition prepared according to the method of claim 8.
MXPA/A/1998/007738A 1996-03-22 1998-09-22 Composition concentrated fabric softener conveyor recovery of freezing / defrosting and composite fabric softener highly unsaturated for im MXPA98007738A (en)

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Application Number Priority Date Filing Date Title
US08620515 1996-03-22

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MXPA98007738A true MXPA98007738A (en) 1999-04-06

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