US 3634260 A
Description (OCR text may contain errors)
United States Patent Office 3,634,260 Patented Jan. 11, 1972 3,634,260 BLEACHING PACKETS John Harlan Pickin, Madison, N.J., assignor to Colgate- Palmolive Company, New York, N.Y.
No Drawing. Continuation of application Ser. No. 647,623, June 21, 1967, which is a continuation of application Ser. No. 502,508, Oct. 22, 1965, which in turn is a continuation-in-part of application Ser. No. 172,104, Feb. 9, 1962. This application Feb. 9, 1970, Ser. No. 9,109
Int. Cl. Clld 7/54 US. Cl. 252-95 6 Claims ABSTRACT OF THE DISCLOSURE A packet for chlorine-containing bleach compositions wherein the composition is enveloped by a film of polyvinyl alcohol prepared by the hydrolysis of polyvinyl acetate and which film contains from about 12-40% by Weight of unhydrolyzed vinyl acetate.
This application is a continuation of copending application Ser. No. 647,623 filed June 21, 1967, now abandoned which application is a continuation of application Ser. No. 502.508 filed Oct. 22, 1965, now abandoned which application is a continuation-in-part of copending application Ser. No. 172,104 filed Feb. 9, 1962, now abandoned.
The present invention relates to packets of bleaching powder. More particularly, it relates to water soluble packets which contain a water soluble bleaching powder.
In accordance with the present invention, a bleaching packet comprises a water soluble packet of polyvinyl alcohol film enveloping a dry, water soluble composition which liberates hypochlorite chlorine on contact with water. It is especially advantageous to have present in the packet an olefin having a double bond containing a tertiary carbon atom, and preferably, the instant packets will also contain an organic detergent or wetting agent, a water soluble inorganic salt, an optical brightening agent, and/or a bluing agent, e.g., ultramarine blue, each of which is stable in the presence of thehypochloritegenerating agent during both storage and use.
The dry composition within the instant packets comprises a dry water soluble compound which, on contact with water, liberates hypochlorite chlorine, said compound preferably constituting about 1 to 90% by weight of the composition, the remainder, i.e., to 99%, being a water soluble diluent therefor such as a Water soluble inorganic salt. The inorganic salts used suitably are those alkaline bufier salts which do not react deleteriously with the hypochlorite-generating agent during either storage or use.
The instant packets offer the advantage of providing a highly effective chlorine-type bleaching agent in a dry form. These packets avoid the dustiness of powdered products, and the likelihood or dangers of spillage or splattering characteristic of liquid products. In use, the entire packet is dropped into a washing machine containing water and clothes to be bleached without any need for premeasuring by the housewife.
The instant packets also avoid the necessity for handling of bulky or heavy containers of glass or fiberboard cartons by the housewife and provide an effective means of masking the characteristic and sometimes irritating odor of chlorine-liberating bleaches. Moreover, use of the packets of the instant invention eliminates the possibility of contact of the hypochlorite-liberating bleach with the skin of the user, which is especially desirable in cases of those people who are allergic to hypochlorites.
The instant packets offer the further outstanding advantage that the product container, i.e. the polyvinyl alcohol film in envelope form, contributes considerable soil-anti-redeposition properties to the system and thus the instant packets are especially suited for use in conjunction with soap and detergent products in connection with the washing and bleaching of soiled clothes. The use of water soluble polyvinyl alcohol film is also advantageous in that it is thermoplastic and may readily be heat sealed, it offers high resistance to permeability by gases, it has excellent oil and grease resistance, long shelf life, and it can easily be printed with alcohol-type inks.
'It is found that the commonly used film forming materials such as methyl cellulose, carboxymethyl cellulose, polyethylene glycol and ethoxylated polyvinyl alcohol become insoluble when left in contact with a strong bleach composition especially those of the type which liberate hypochlorite chlorine or other chemicals which cause the film forming material to become insoluble. The above described film forming materials are, therefore, undesirable for use with bleaching compounds of the type claimed herein.
As indicated above, the polyvinyl alcohol film employed in the preparation of the instant packets is water soluble, that is, with mild agitation it dissolves substantially completely in water at temperatures of from about to F. within about 30 seconds. Commercial polyvinyl alcohol which is prepared by the hydrolysis of polyvinyl acetate may be employed, however, it has been found highly desirable to avoid the use of water soluble polyvinyl alcohol which has been ethoxylated, i.e. reacted with ethylene oxide, inasmuch as such ethoxylated polyvinyl alcohol appears to be less stable on aging and storage in contact with the instant hypochlorite generating agents than does material which is free from ethoxylation. Polyvinyl alcohol which is devoid of ethoxylation and contains on the order of from about 12 to 40 percent by weight of unhydrolyzed vinyl acetate constituents has been found to be exceptionally stable towards the hypochlorite liberating agent during storage and use and to possess highly desirable flexibility characteristics and solubility characteristics in both hot (140 F.) and cold (80 F.) water.
Hypochlorite generating agents suitable for use in the packets of the present invention are those water soluble dry solid materials which generate hypochlorite ion on contact with, or dissolution in, water. Examples thereof are the dry, particulate heterocyclic N-chlor imides such as trichlorocyanuric acid, dichlorocyanuric acid, and salts thereof such as sodium dichlorocyanurate and potassium dichlorocyanurate. Other imides may also be used such as N-chl0rosuccinimide, N-chloro malonimide, N-chloro phthalimide and N-chloro naphthalimide. Additional suitable imides are the hydantoins such as 1,3-dichloro- 5,5-dimethyl hydantoin; .N-monochloro-C,C-dirnethylhy dantoin; methylene-bis (N-chloro C,C dimethylhydantoin; 1,3-dichloro 5 methyl-5-isobutyl-hydantoin; 1,3- dichloro-S-methyl 5 ethylhydantoin; 1,3-dichloro-5,5 diisobutylhydantoin; 1,3 dichloro-S-methyl-S-n-amylhydantoin, and the like. Other useful hypochlorite-liberating agents are trichloromelamine and dry, particulate, water-soluble anhydrous inorganic salts such as lithium hypochlorite and calcium hypochlorite. Normally, the instant chlorine-liberating agents are employed in a proportion, within the range indicated above, such as to yield a product which contains from about 1 to about 20% available chlorine on a total weight basis, although other proportions may be employed if desired.
It has been found that the formation of insoluble material during extended storage and aging of polyvinyl alcohol bleach packets which contain the instant hypoilorite generating agents may be alleviated by the presice, in such packets, of an olefin having a double bond )ntaininga tertiary carbon atom. The use of such an .efin, in a packet prepared from the preferred acetate- )ntaining polyvinyl alcohol film, facilitates the preparaon of packets having long shelf life without undergoing lrmation of insoluble material.
The olefins employed to diminish the formation of in- )luble products in the packets of the present invention ave a carbon-to-carbon double bond in which one of the rrbon atoms is tertiary, i.e., is directly attached to a total three carbon atoms, one sharing the double bond and v0 others in addition. These olefins readily undergo hypoilorous acid addition, their unsaturation being not exusively of an aromatic or benzenoid nature. The instant .efins may be cyclic or acyclic, e.g., parafiinic or cycloiraffim'c, and the tertiary carbon-containing double bond ray be terminal (in 1,2 position), or it may be nonrminal or part of a cyclic structure. The instant olefins .ay be liquid or solid at room temperature, it being pre- =rred to employ those with arelatively low vapor pres- 4 sulfonic acids, e.g. fatty acid esters of the sodium salt of isethionic acid; the fatty ethanolamide sulfates; the fatty acid amides of amino alkyl sulfonic acids, e.g. lauric acid amide oftaurine; as well as numerous other ionic organic surface active agents such as sodium toluenesulfonate, sodium xylenesulfonate, sodium naphthalene sulfonate; and mixtures thereof. In general these organic surface active agents are employed in the form of their alkali ire (e.g. having a boiling point at one atmosphere above nout 125 C. and preferably in the range from 150- )0 C.).
The preferred olefins constitute odoriferous terpenes lCh as those isoprenoid hydrocarbons containing two or tore, usually from two to six, isoprene units in a cyclic acyclic structure, ie terpenes, sesquiterpenes, diter :nes, triterpenes, and the like which broadly may be re- :rred to as terpenes. Specific examples of suitable such rpenes are alpha-phellandrene, p-menthene1, p-mentene-3, alpha-terpinene, terpinene, terpinolene, terpinyl :etate, terpineol, alpha-pinene, beta pinene, pulegone, locimene, 'linalyl acetate, neryl acetate, camphene, and .ixtures thereof including naturally occurring materials [Ch as geranid, pine oil, pine-needle oil, orange terpenes, 1d oil of cedarwood. It is especially preferred to employ 1e normal liquid polyunsaturated terpenes containing at ast two isoprenoid units, such aslimonene and myrcene, these materials have been found to be particularly suitmetal salts or alkaline earth metal salts as these'salts possess the requisite stability, solubility, and low cost essential to practical utility.
Amphoteric or cationic detergents may also be employed in the instant packets, examples thereof being sodium N-lauryl beta alanine and cetyl pyridinum chloride respectively.
The proportion of organic surface active agent which is used may vary widely, typically being from about 1 to 30% by weight of the composition contained within the packet.
The presence of inorganic salts in the instant bleachsuch as sodium bisulphate. The presence of sodium carbonate or sodium metasilicate in the instant packets has been found to aid in the retention of the water soluble characteristics of these packets, sodium carbonate being especially beneficial in that on dissolution in water, it reacts with any acidic components present (e.g. in the hy- 71c and effective in the packets of the present invention.
Other olefins having a double bond containing a terti- 'y carbon atom which may be employed in the packets F the present invention include polymerized isobutylene, g. diisobutylene, polymerized propylene, e.g. propylene tramer, and 5-butyl-4-nonene such as may be convenientprepared by dehydration of tributylcarbinol.
The proportion of the olefin employed in the packets the instant invention typically constitutes about 0.1 to by weight of the hypochlorite-generating agent which present.
Surface active agents suitable for use in the instant lckets include a wide variety of water soluble organic :tergents and wetting agents stable in the presence of e hypochlorite generating agent. Such detergents may anionic detergent salts having alkyl substituents 0f 8 to 5 carbon atoms such as the water soluble higher fatty :id alkali metal soaps, e.g. sodium myristate and sodium ilmitate; water soluble sulfated and sulfonated anionic kali metal and alkaline earth metal detergent salts conining a hydrophobic higher alkyl moiety (typically conining from about 8 to 22 carbon atoms) such as salts higher alkyl monoor poly-nuclear aryl sulfonates havg from about 10 to 16 carbon atoms in the alkyl group =.g. sodium dodecylbenzene sulfonate, magnesium tri- :cylbenzene sulfonate, lithium or potassium pentapropyl- 1e benzene sulfonate); alkali metal salts of higher alkyl tphthalene sulfonic acids; sulfated higher fatty acid onoglycerides such as the sodium salt of the sulfated onoglyceride of coconut oil fatty acids and the potas- Jm salt of the sulfated monoglyceride of tallow fatty :ids; alkali metal salts of sulfated fatty alcohols containg from about 10 to 18 carbon atoms (e.g. sodium lauryl lfate and sodium stearyl sulfate); alkali metal salts of gher fatty acid esters of low molecular weight alkylol pochlorite generating agent) to produce bubbles of carbon dioxide gas which contributes a desirable mixing and agitating action..
A highly desirable constituent of thecomposition within the instant packets is a fluorescent brightener or optical dye which is stable in the presence of the hypochlorite generating agent. Such brighteners are of particular assistance in connection with the bleaching of textiles or fabrics in those instances where the chemical bleaching power of the contents of the instant packets may beneficially be supplemented by the action of a blue fiuorescing optical bleach. Examples of suitable such textile-substantive optical bleaches, which may be present in amounts on the order of about .01 to 1 percent by weight of the packets, are triazole compounds such as N S 0 H and sulfonated 3,7-diaminodibenzothiophene dioxides such as -SO H Although for convenience the acid forms of these compounds are depicted, it will be appreciated that these formulas as used herein are also indicative of suitable salts thereof compatible with the remaining constituents of the inst-ant product, such as, erg. the sodium salts.
The packets of the present invention optionally may also contain suitable proportions, i.e. on the order of 0.1
to 1 percent by weight thereof, of hypochlorite-stable, nonsubstantive bluing agent such as ultramarine blue. (It will be appreciated, especially in connection with such bluing agent which is a Water insoluble pigment, that for the purposes of this invention, materials which are not truly water soluble may be present as long as they are Water dispersable in normal use of the instant packets.)
The presence in the compositions contained within the instant packets of an agglomerating or dust-laying agent which is stable in the presence of hypochloride generating agent, such as mineral oil, is also highly desirable inasmuch as it diminishes the formation of dust by the composition, thereby facilitating manufacture of the packets, particularly the step of sealing the film. Suitably mineral oil may be added in proportions of 0.1 to 1.5%, 0.25% normally being adequate to achieve effective dust-laying action.
The resistance of the instant packets towards the formation of insoluble material during storage may be improved by sealing these packets within a moisture impermeable container, such as a metal foil or metal foil covered paperboard box land/ or within a plastic film characterized by an extremely low moisture vapor transmission rate, e.g. polyethylene; laminates of polyethylene, aluminum foil, and glassine, or wax-coated laminates of metal foil and glassine. A preferred reclosable container which is substantially impermeable to moisture vapor constitutes a bag of polyethylene or like film which is sufficiently large that the open end may be multiply folded over on itself to provide a substantially moisture vapor tight seal. Such a bag having a folded closure may be placed within a more rigid container or otherwise be provided with means to prevent unravelling of the folded portion of the bag.
The compositions within the instant packets should be dry, i.e., desirably they contain less than 1% and preferably less than 0.5% moisture, in order to prevent decomposition of the hypochlorite liberating agents prior to use of the packets. Various adjuvants may, however, be present including, inter ali-a, organic sequestrants such as ethylene diarnine tetraacetic acid and its salts, sodium carboxymethyl cellulose, citric acid, resins and polymers such as polyvinyl pyrrolidone, polyacrylates and the like, starch, urea, perfumes, corrosion inhibitors, coloring matter, and the like. Adjuvants to be added to the instant packets may, where appropriate, be incorporated in the film itself in addition to or in lieu of being part of the composition within the packet.
The following examples are given additionally to illustrate the nature of the invention and it will be understood that the invention is not limited thereto. All parts or percentages are by weight unless otherwise indicated, and unless specifically denoted to be otherwise, the components employed are substantially completely dry or anhydrous.
EXAMPLE I The following composition is dry mixed in a rotating drum, the perfume and limonene being sprayed into the drum as the last two constituents to be added:
d-Limonene Approximately 42 grams of the foregoing composition are sealed in a packet or envelope made of a cast 1 /2 mil thick film of polyvinyl alcohol prepared by hydrolysis of polyvinyl acetate and containing about by weight of polyvinyl acetate. This polyvinyl is free from ethoxylation. The film is heat sealed to form a packet 'which consists of a centrally folded sheet of cast film heat sealed along three edges (two of which are heat sealed prior to filling and one subsequently thereto).
The packet is then packed within an aluminum foil covered paperboard container which helps to protect the packet from exposure to moisture vapor during storage prior to use.
EXAMPLE II The following constituents are dry blended in the proportions indicated, the limonene, perfume, and white mineral oil being sprayed on the other constituents of the formula while they are tumbled:
About 40 grams of the above dry blend are heat sealed within an envelope of the water soluble polyvinyl alcohol film of Example I. The envelope, when empty, measures 6 by 9 centimeters (the weight ratio of dry mix to envelope being 98.16:1.84). Ten of these packets are placed in an airtight pouch of polyethylene film 0.0045 inch thick which pouch has one open end. The open end of the pouch is multiply folded to provide an air and vapor tight reclosable seal, and the closed pouch is packaged in an aluminum-foil covered cardboard box which provides additional protection from atmospheric moisture vapor.
EXAMPLES III-V The following dry formulations may be employed in the manufacture of packets in lieu of the formulations given in Example II:
Percent Example III IV V Pentasodium tripolyphosphate 30. 56 10. 19 10. 19 Alkyl aryl sulfonate (contains 76% sodium tridecylbenzene sulfonate, 9.9% Sodium silicate, 10.8% sodium sulfate, and 3.3%
moisture) 3. 71 3. 71 3. 71 Sodium carbonate 5. 09 Sodium metasilicate. 10. 19 10. 19 Sodium sulfate 44. 79 61. 59 Bleach stable fluorescent brightener of Example II 0.16 0.16 0.16 Perfume 0. 25 0. 25 0. 25 d-Limonene 0. l6 0. 16 0. 16 Potassium dichloroeyanurate 15. 28 13. 75
Sodium chloride Packets produced in accordance with Examples III-V are packed in groups of 10 each in an air-tight reclosable container fabricated of 0.00035" aluminum foil glued with two pounds of glue per 3,000 square feet to pouch paper weighing twenty five pounds per 3,000 square feet, the aluminum foil being coated on its unglued surface with 0.001 inch thick polyethylene.
EXAMPLE VI The following constituents are dry blended:
Potassium dichlorocyanurate 15.25 Pentasodium tripolyphosphate 20.00 Fluorescent brightener of Example II 0.16 Sodium sulphate 64.59
Forty grams of the above blend are placed in a packet easuring 5.7 by 8 centimeters prepared from east water -luble polyvinyl alcohol film free of ethoxylation.
EXAMPLE VII The following constituents are dry blended:
Parts )dium sulphate 66.13 :ntasodium tripolyphosphate 20.00 etergent of Example I 3.71 luorescent brightener of Example II 0.16 richlorocyanuric acid 10.00
This dry blend is packed in polyvinyl alcohol film to rm packets as in Example II.
EXAMPLES VIIIXII Parts by weight 81111310 VIII IX X XI XII dium sulfate 72 72 85 88.6 88.9 thiuni hypochlorite ilcium hypochlorite i-dichloro-5,5-dimethyl hydanto 'ichlorornelamine 'ichlorocyanuric acid Limonene 1.25 1. 25
40 grams of each of the indicated compositions are heat aled between square sheets of the polyvinyl alcohol film Example I measuring approximately centimeters on .ch side. The sheets are heat sealed together on all four argins.
EXAMPLE XIII A dry mix of the following materials is prepared:
Percent :ntasodium tripolyphosphate 86.37 monene 0.32
:rfume .50 )tassium dichlorocyanurate 12.81
This dry composition is sealed within envelopes of ater soluble polyvinyl alcohol film to form water soluble rckets which are then packaged in groups of six or more a moisture tight container. If desired, the polyvinyl cohol film employed may be colored, e.g. blue, green, the like, instead of the conventional clear material.
EXAMPLE XIV A dry mixture of the following constituents is prepared:
The composition is prepared by spray drying an aqueous lrry of the first six constituents and the sodium sulfate form spray dried beads thereof. These beads are then mbled in a drum and the limonene constituent is sprayed ereon. After tumbling for five minutes subsequent to 2 addition of the limonene, the trichlorocyanuric acid nstituent is added and mixing is continued for an addimal five minutes at which time the perfume is sprayed to the product and mixing is continued for an additional enty minutes. After mixing is complete, water soluble ckets are prepared by heat sealing 21 grams of the mposition within envelopes of commercial water soluble lyvinyl alcohol containing about 3% of vinyl acetate 8 and 10% by weight of combined ethylene oxide. These packets are packaged eight or nine to a box, in cardboard boxes measuring 6.4 x 6.6 x 20 centimeters, the boxes being Wrapped in a sheet of aluminum foil which is sealed along its outer exposed edges with masking tape.
EXAMPLE XV The following composition is prepared in particulate form by spray drying an aqueous slurry of the constituents therein:
Parts per weight Sodium tridecylbenzene sulfonate 27.50 Pentasodium tripolyphosphate 39.20 Sodium carboxymethyl cellulose 0.41 Organic corrosion inhibitor 0.10 Fluorescent brightener of Example II 0.09 Sodium silicate 7.00
Moisture 3.05 Sodium sulfate Balance to 100 These particles are tumbled in a rotary drum and sprayed with a mixture of equal parts of perfume and camphene in a ratio of 2.8 grams to 1,000 grams of the spray dried particles. Subsequently 18 grams of finely pulverized trichlorocyanuric acid are added for each 1,000 grams of the spray dried particles. After complete mixing has occurred, the composition is heat sealed Within envelopes of water soluble polyvinyl alcohol to form highly effective bleaching packets. The packets are placed in a cardboard box which is covered with an outer seal of aluminum foil.
EXAMPLES XVI AND XVII Bleaching packets are prepared by heat sealing 40 grams of the following composition between two 5 centimeter square sheets of Water soluble polyvinyl alcohol film which is free of ethoxylation and which contains 15% vinyl acetate.
Example XVI XV I I Trichlorocyanuric acid, percent 1O Pentasodium tripolyphosphate, percent 25 EXAMPLE XVIII A bleaching packet containing both fluorescent brightener and bluing is prepared by heat sealing 40 grams of the following dry mixture between two rectangular sheets of cast water soluble polyvinyl alcohol film measuring 7.5 by 3.7 centimeters and 1.5 mils thick. The polyvinyl alcohol is prepared by hydrolysis of polyvinyl acetate and contains 15% of unhydrolyzed vinyl acetate. It is free of ethoxylation, and dissolves substantially completely in water with mild agitation within 30 seconds at both 80 F. and F.
Dry mixture: Parts Pentasodium tripolyphosphate 30.00 Sodium carbonate 5.00 Sodium sulfate, anhydrous 40.69 Fluorescent brightener of Example II 0.16 Ultramarine blue 0.30 Alkyl aryl sulfonate of Example III 2.62 Perfume 0.25
Limonene 0.25 Potassium dichlorocyanurate 20.60 Mineral oil 0.13
The weight ratio of the dry mixture to the polyvinyl alcohol film in the final packets is 98.81 to 1.19.
The packets are packed, in groups of 10, in an open ended flattened cylindrical bag of polyethylene film 1.5 mils thick and measuring 15 by 21 centimeters. The bag is open at one end and this end of the bag is multiply folded over on itself to provide a reclosable air and moisture-tight container. The bag of packets is in turn packed Within an aluminum foil covered cardboard carton having a hinged, reclosable top opening. The carton prevents the folded bag from unrolling and coming open during the time the bag of packets is stored therein.
While there has been disclosed that which at present is considered to be the preferred embodiment of the invention, it will be understood, of course, that changes, modifications, or substitutions may be made therein without departing from the true scope of the invention as defined in the appended claims.
What is claimed is:
1. A bleaching packet consisting essentially of a water soluble packet of polyvinyl alcohol film devoid of ethoxylation prepared by the hydrolysis of polyvinyl acetate and containing from about 12 to 40% by weight of unhydrolyzed vinyl acetate, said film enveloping a dry composition consisting essentially of 1 to 90 percent by Weight of a water soluble chlorine-containing compound which liberates hypochlorite chlorine on dissolution in water and 10 to 99% of a water soluble diluent therefor which is inert thereto in both dry condition and in aqueous solution.
2. A bleaching packet as set forth in claim 1 in which said diluent is sodium carbonate.
3. A bleaching packet as set forth in claim 1 in which said chlorine-containing compound is a heterocyclic N- chloroimide.
4. A bleaching packet as set forth in claim 3 in which said N-chloroimide is selected from the group consisting of polychlorocyanuric acids and salts thereof.
5. A bleaching packet as set forth in claim 3 in which said N-chloroimide is potassium dichlorocyanurate.
10 6. A bleaching packet as set forth in claim 1 and which further contains fluorescent brightener which is a triazole compound of the formula Us. (:1. X.R.