CA1332336C - Toilet bowl cleaner - Google Patents
Toilet bowl cleanerInfo
- Publication number
- CA1332336C CA1332336C CA000616543A CA616543A CA1332336C CA 1332336 C CA1332336 C CA 1332336C CA 000616543 A CA000616543 A CA 000616543A CA 616543 A CA616543 A CA 616543A CA 1332336 C CA1332336 C CA 1332336C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- composition
- cleansing block
- polyethylene glycol
- block composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Detergent Compositions (AREA)
Abstract
ABSTRACT
TOILET BOWL CLEANER
Solid cake lavatory cleansing block compositions comprise polyethylene glycol distearate having a dissolution time of at least 5.5 hours, a non-ionic surfactant, a water-soluble salt filler and optional ingredients which include a gelling natural gum, fragrances; dyes, solid binders, filler material and mixtures thereof.
TOILET BOWL CLEANER
Solid cake lavatory cleansing block compositions comprise polyethylene glycol distearate having a dissolution time of at least 5.5 hours, a non-ionic surfactant, a water-soluble salt filler and optional ingredients which include a gelling natural gum, fragrances; dyes, solid binders, filler material and mixtures thereof.
Description
~33233~
TOILET BOWL CLEANER
The present invention relates to cake compositions which are useful for the treatment of the flush water of toilets. More particularly, the invention i5 concerned with a long lasting toilet tank dispenser which may be formed by casting and is responsive to the flushing of the toilet.
This application is a divisional of copending Canadian patent application Serial No. 540,143 filed June 19, 1987.
In treating toilet flush water with chemicals in order to produce desirable effects such as bowl aesthetics, cleaning, disinfection, deodorization, aerosol reduction, etc., it is desirable that the 15 che~icals be dispensed into the flush water automatically each time the toilet i8 flushed. The prior art discloses numerou~ devices which have been designed for this purpose.
Particularly desirable devices are those comprising 20 a solid cake composition. In this type of device, a measured amount of water enters the device during one flush cycle and remains in contact with the cake between flushes, thereby forming a concentrated solution of the composition which i8 dispensed into the flush water ~` 25 during the next flush. The advantages of such devices are that the chemical composition can be packaged and shipped in more concentrated form than aqueous solutions of the chemicals. Also, the problems of liquid spillage resulting from breakage of the dispensers during shipment 30 or handling is eliminated.
s Prior art surfactant cake compositions are disclosed in U.S. 4,308,625 (Kitko) and U.S. 4,043,931 (Jeffrey et al). These patents disclose a lavatory cleansing tablet which is formed with two or more non-ionic surfactants 35 which incIudes the use of polyalkoxylated alcohols.
-` ~33233~
U.S. 4,477,363 (Wong et al) discloses a solid cake comprising free fatty alcohol and a buffered alkali earth metal alkyl sulfate surfactant.
JP 58-168699 (Japan Synthetic Rubber Co. et al) discloses a cast lavatory cleansing block containing 25 to 90 weight % of a mixtuxe of polyethylene glycol or monoester thereof and polyethylene glycol diester. The preferred monoester and diester are the stearates and the exemplified stearates are polyethylene glycol 4000 and 6000 monostearates and polyethylene glycol 6000 distearate. The block may also contain inter alia a deodorizing agent, detergent, colorant, filler, binder, aromatic, and dissolution rate adjuster.
JP 58-25398 (Lion) discloses a cast lavatory cleansing block containing 40 to 98 weight % of polyethylene glycol diester, preferably distearate.
Especially preferred diesters are polyethylene glycol 1500, 3000 and 9000 distearates. The block may also contain inter alia aromatic, colorant, surface-active agent, ger~icide, and builder.
JP 59-24797 (Earth I) discloses a cast lavatory cleansing block containing at least 40~ of a polyethylene glycol distearate having 91 to 230 moles ethylene oxide adduct groups and 0.1 to 60% of either polyoxyethylene sorbitan monositearate, 6 ethylene oxide or polyethylene sorbitan tristearate, 20 ethylene oxide. Exemplified polyethylene glycol distearates have 91, 160, 230 and 245 moles ethylene oxide. The block may also contain inter alia dye and fragrance.
JP 61-83300 (Earth II) discloses a cast lavatory cleansing block containing 1-8 volume % 12-hydroxy stearic acid and/or 0.1-5% benzylidene sorbitol, 20-70%
perfume; 10-30% coloring matter; and 15-60% surface active agent. The surface active agent can comprise a polyethylene glycol distearate. The block may also contain inter alia deodorant, bactericide and chlorine-remover.
~ .
~ v~
3 ~33233~
u.s. 4,269,723 (sarford et al I) discl~ses a compressed lavatory cleansing block containing one or i~
more organic surface active agents and one or more binders which binder(s) act as dissolution retarding agents and are selected from clays and water-soluble and water-dispersible gel-forming organic polymeric materials. Specified binders include alginates and carragheenates and specified surface active agents include alkylene oxide condensates of fatty acids.
G.B. 2,061,g96 A (Jeyes) is substantially the same as Barford et al I except that the block is formed by melting lower-melting point components, dispersing higher melting point and/or liquid components in the melt, and then casting into a mould.
U.s. 4,460,490 (Barford et al II) discloses a bi-component lavatory cleansing block comprising a shaped body formed of a slow-dissolving cleansing composition containing at least one surface active agent and a tablet comprising a bleaching agent embedded in or adhered to the shaped body. The shaped body preferably comprises one or more readily-soluble surface active agents in admixture with one or more solubility control agents.
Specified solubility control agents include low ethoxylates of fatty acids and gel-forming gums, such as xanthan gum, or materials, such as alginates or - carragheenates.
U.S. 4,310,434 (Choy et al) and U.S. 4,278,571, (Choy) disclose surfactant cake compositions containing ~; dyes and perfumes which are utilized in the present invention. The surfactants provide cleaning and sudsing in the toilet bowl and also serve to dispense other components of the compositions such as dyes, perfumes, organic resins, etc.
Water-soluble inert salts such as alkali metal chlorides and sulfates are used in such compositions to act as a "filler" so that the composition can be formed ,: :
~ A
.`~ .
4 ~ 3 ~
into cakes of desirable size without using excessive amounts of active ingredients. The predominant ingredients of the cake compositions are usually the surfactant, perfume and the filler salt.
A major problem in this art has been short and/or erratic longevity of surfactant cakes because of rapid and uneven dissolution resulting in decreased cake stability and longevity.
It has been found that a cast solid cake composition which has a long and uniform block life can be provided where the composition comprises a polyethylene glycol distearate if said distearate has a specific water solubility and molecular weight range.
The present invention is directed towards the provision of a solid cake which may be formed by casting and comprises a specific kind of polyethylene glycol distearate, which compositions are suitable for use for automatically dispensing cleansing agent~ into the toilet, particularly a cast solid cake composition having relatively high melt temperatures and less block surface tackine6s for improved processing.
The present invention is further directed towards the provision of a lavatory block which has a long and uniform block life that eliminates sluggish toilets and which resists mounding and major fragmentation.
In accordance with the present invention, there is provided a solid cake lavatory cleansing block composition, which comprises (i) about 8 to about 35% by weight of the composition of a polyethylene glycol distearate having a drop dissolution time of at least about 5.5 hours according to the Distearate Dissolution Test (see Example 1 hereinafter) and a molecular weight from about 3,000 to 12,000, preferably about 7,000 to 9,000, (ii) about 20 to about 64% by weight of the composition of a water-soluble salt filler, and (iii) up to about 40% by weight of the composition of a non-ionic surfactant. Optional ingredients are selected from the j"
~`` 5 133233~
groups consisting of fragrances, dyes, binders, filler materials and mixtures thereof. As noted above, the cake composition comprises from about 8% to about 35%, preferably about 12% to 29%, by weight of said polyethylene glycol distearate. It is known that polyethylene glycol distearate is extremely hydrophilic.
Because of the extreme hydrophilic nature of the compound, it would be expected that the material would be very water soluble without any prolonged transition from solid to a liquid. It has been surprisingly found that the particular kind of polyethylene glycol distearate of the invention goes through a hydration stage forming a tenacious gel so as to provide the aforementioned extended block life relative to other formulations containing polyethylene glycol distearate of varying molecular weights.
It is critical in the present invention that the polyethylene glycol distearate which is utilized in the formulation of the cake composition has a drop dissolution time of at least about 5.5 hours according to the Distearate Dissolution Test. It has been found that not all polyethylene glycol distearates having a molecular weight of about 3,000 to 12,000 possesses such a characteristic. Their method of preparation appears to influence their solubility. Preferably, their ~ preparation is according to the method of condensing a ^~ fatty acid with an alcohol as described by W.B. Satkowski ; et al in HPolyoxyethylene esters of Fatty Acids", ionic Surfactants M.J. Schick Ed. (Dekker, ~Y 1967) p.
142-17A. For example, stearic acid having a molecular weight of 284.5 is reacted with a polyethylene glycol having a molecuIar weight range between 5500-8500 to form a polyethylene glycol distearate having a molecular weight range of about 6033-9033. Such compound having a dissolution time of at least 5.5 hours is suitable for use in the invention.
.~
, :, .~
~332336 In order to improve the cake characteristics, it has been found advantageous to utilize in the cake composition a greater portion of polyethylene glycol distearate which has a molecular weight betwe0n about 7,000 to about 12,000. A lesser portion of polyethylene glycol distearate having a molecular weight between about 3,000 to about 7,000, preferably about 3,000 to about 4,000 in combination with the higher molecular weight polyethylene glycol distearate aids in preventing mounding and further acts as a binder.
The compositions of the invention also comprise a non-ionic surfactant. Non-ionic surfactants that may be included are the condensation products of a long chain ethylene oxide moiety with an aliphatic alcohol, preferably a primary or secondary aliphatic alcohol, or an alkyl phenol. Preferably the primary and secondary alcohol contains 8 to 20 carbon atoms and the alkyl phenol-based moiety is one wherein the alkyl chain is straight or branched and contains 6 to 12 carbon atoms, 2~ preferably 6 to 9 carbon atoms.
Illustrative non-ionic surfactants having the desired characteristics for foxmulation are available on the market under the Trade Marks "Neodol" (Shell Oil Co~pany); "Tergitol" (Union Carbide Company); and "Alfol"
(Continental Oil Company). Specific examples include "Neodol 25-7" (linear C12-C15 primary alcohol condensed with 7 moles of ethylene oxide per mole of alcohol);
"Neodol 45-7" (linear C14-C15 primary alcohol condensed with 7 moles of ethylene oxide per mole of alcohol);
"Tergitol 15-S-7" (random secondary C11-C15 alcohol condensed with 7 moles of ethylene oxide per mole of alcohol); and "Alfol 1416-6.5" (primary C14-Cl6 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol).
Such non-ionic surfactants act as coupling agents to provide an integration of the cake components and may be :
~,,; ~ ~ , ~ t3323~
used in the amount of up to about 40%, preferably about 20 to about 30%, by weight of the cake formulation.
Also useful to enhance the life of the cake are ethoxylated nonylphenols. The high ethoxylated nonylphenols, that is those having over 20 moles of ethylene oxide per mole of phenol, provide slow dissolution of the cake formulation. Up to about 10%, preferably up to 5~, by weight of ethoxylated nonylphenols is prePerably utilized together with the ethoxylated aliphatic alcohols.
Water-soluble inert salts are used in the present compositions as "fillers" so that the composition can be formed into cakes of desired size without using excessive amounts of active ingredients. They are used alone or in combination in amounts up to about 64% by weight.
The inert salts (filler salts) used in the compositions of the present invention can be any water-soluble inorganic or organic salt or mixtures of such salts. For purposes of the present invention, "water-soluble" means having a solubility in water of at least 0.2 grams per hundred qrams of water at 20C. Examples of suitable salts include various alkali metal and/or alkaline earth metal sulfates, chlorides, borates, bromides, citrates, acetates, lactates, etc.
Specific examples of suitable salts include calcium sulfate, sodium chloride, potassium sulfate, sodium carbonate, lithium chloride, tripotassium phosphate, sodium borate, potassium bromide, potassium fluoride, sodium bicarbonate, calcium chloride magnesium chloride, sodium citrate, sodium acetate, calcium lactate, .~ j .
magnesium sulfate and sodium fluoride. The preferred salts are the inorganic salts, especially the alkali metal sulfates and chlorides. Particularly preferred salts, because of their low cost, are calcium sulfate and sodium chloride. The salts are present in the compositions herein at levels of from about 20% to about ~ ~ 64% by weight, preferably from about 20% to about 35%.
"~
: ` ~
~33~
Most preferably, sodium chloride i6 utilized togetherwith guar gum (binder) either alone or with other salts since the combination not only provides a synergistic viscosity increase of water and decreases the relative solubility properties of the matrix in water but also aids to prevent mounding.
Calcium sulfate is advantageously utilized alone or together with other natural gum binders or together with sodium chloride because it has a low solubility level which is constant over the water temperature range likely to exist within toilet tanks.
It has been found that natural gums can advantageously be utilized as binders in the present invention. The natural gums ~hich may be utilized are those which arc cold water gelling additives and develop a high viscosity and a high gel strength. Included in the gums which may be utilized are guar, xanthan, tragacanth, carrageenan, karaya, algin, and the like.
Usually, the gum i8 present in an amount of 3 to 35%, preferably 5 to 15%, by weight of the composition. The most preferable is guar which has been found to be the most effective in retarding block dissolution and to reduce the problem of sluggish toilet behaviour.
As mentioned above, it has been found to be particularly advantageous to utilize guar gun, together with sodium chloride as a filler since there is a synergistic viscosity increase of water that is not found with other fillers such as calcium sulfate.
Additionally, there is an increase of the relative 3Q insolubility properties of the matrix in water.
As a further binding agent, the use of solid emollients have been found to be helpful to prevent the cake of the invention from mounding out. Suitable ~; emollients include glyceryl monostearate, glyceryl monopalmitate, ethylene glycol stearate, propylene glycol monostearate, and the like, most preferably is glyceryl monostearate whiGh provides a matrix to prevent mounding.
.
l ~~
:
11 332~3~
The emollients may be utilized in amounts of up to about 20% by weight, pre~erably about 5% to about 12%.
Variou~ optional materials may be included in the compositions herein.
Dyes may be included at levels of up to 15%, preferably about 2.5% to 10% by weight. Examples of suitable dyes are Alizarine Light Blue B (C.I. 63010), Carta 81ue VP (C.I. 24401), Acid Green 2G (C.I. 42085), Astragon Green D (C.I. 42040), Supranol Cyanine 7B (C.I.
10 42675), Maxilon Blue 3RL (C.I. Basic Blue 80), Drimarine Blue Z-RL (C.I. Reactive Blue 18), Alizarine Light Blue H-RL (C.I. Acid Blue 182), FD&C Blue No. 1, FD&C Green No.3 and Acid Blue No. 9 (C.I. 42090). Others are disclosed in the aforementioned Patent Nos. 4,310,434 and 15 4,477,363.
The cakes of the invention may also contain up to about 15% by weight of a cationic quaternary ammonium salt.
It is known that the cationic quaternary ammonium salts which include a greater number of short-chain alkyl groups in the structure, incline toward better bacteriostatic properties. Speci~ic examples of bacteriostatic agents that may be used in the compositions of this invention include di-isobutyl cresoxy ethoxy ethyl dimethyl benzyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, myristyl dimethylbenzene ammonium chloride, benzalkonium chloride, cetyl pyridinium chloride, coconut dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl diethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium bromide, di-isobutyl phenoxy ethoxy ethyl trimethyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl alkyl ammonium chloride, methyl-dodecylbenzyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, octadecyl dimethyl ethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide, ; ' : ~
-~ 13~23~
octadecenyl-9-dimethyl ethyl ammonium bromide, dioctyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, hexadecynyl trimethyl ammonium iodide, octyltrimethyl ammonium fluoride, and mixtures thereof. Other water dispersible salts, such as the acetates, sulfates, nitrates, and phosphates, are effective in place of the halides, but the chlorides and bromides are preferred.
The cakes may also contain perfumes to impart an acceptable odor to the flushing water. The perfume may be in solid form and is suitably present in an amount up to 15%, preferably up to 10%, by weight. In this connection, it may be noted that the term "perfume" is intended to refer to any material giving an acceptable odor and thus materials giving a "disinfectant" odor such as essential oils, pine extracts, terpinolenes, ortho phenyl phenol or paradichlorobenzene may be employed.
The essential oils and pine extracts also contribute as plasticizers and are functional to a degree in extending block life.
Certain perfume materials may be added which additionally function to control the solubility of anionic sulfate surfactants. Examples of such perfume materials are isobornyl acetate myrtenyl acetate and frenchyl acetate. Other suitable perfume or fragrances are diæclosed in U.S. Patent No. 4,396,522 of Callicott et al.
The cake formulation may also contain other binding and/or plasticizing ingredients serving to assist in the i manufacture thereof, for example, polypropylene glycol having a molecular weight from about 3,000 to about 10,000 in an amount up to about 20% by weight preferably about 4% to about 15% by weight of the mixture may be used. The polypropylene glycol reduces the melt ~; viscosity, acts as a demolding agent and also acts to plasticize the block when the composition is prepared by ',!
.
~'` .
}~" -~ 33233~
a casting process. Other suitable plasticizers such as pine oil fractions, d-limonene, dipentene and the ethylene oxide-propylene oxide block copolymers may be utilized.
The blocks of the present invention can be produced by a variety of processes, e.g., casting/moulding process, by tablet compression process or by an extrusion process. The casting process being the prefèrred process of the invention.
The casting process which is well within the skill of those in the art involves the melting of the ingredients and then casting the melt into appropriate shaped moulds and allowing the mel~ to cool and solidify.
The shaped tablets or blocks each suitably have a weight of from 20 to 150 grams, preferably from 30 to 70 grams.
In one preferred embodiment, the compositions of the invention comprise from 8 to 35% by weight of the polyethylene glycol distearate; up to 40% by weight of the non-ionic surfactant; up to 64% by weight of water-so}uble salt filler; and at least one of:
(a) up to 35% by weight of a gelling natural gum;
(b~ up to 20% by weight of a solid emollient binding agent;
(c) up to 10% by weight of an ethoxylated nonylphenol;
(d) up to 15% by weight of a dye;
(e) up to 15% by weight of a cationic quaternary ammonium salt;
(f) up to 15% by weight of a perfume; and (g~ up to 20% by weight of a plasticizer.
In one especially preferred embodiment, said preferred compositions comprise 20 to 30% by weight of an ethoxylated C8-C20 aliphatic alcohol, up to 32% by weight -~
of sodium chloride and/or up to 32% by weight of calcium - sulfate, from 4% to 15% by weight of plasticizer, and at -~
l-ast one of~
up to 10% by weight of glyceryl monostearate; ~-~
up to 10% by weight of ethoxylated nonylphenol;
12 ~l 3 ~
up to 35% by weight of guar gum; and up to 15% of disinfecting agents, coloring and/or fragrances.
In another especially preferred embodiment, said preferred composition comprises:
(a) from 12 to 29% by weight of the polyethylene glycol distearate;
(b) 5 to 15% by weight of a gelling natural gum;
(c) 5 to 12% by weight of a solid emollient binding agent;
(d) 20 to 30% by weight of a non-ionic surfactant;
(e) optionally, up to 10% by weight of an ethoxylated nonylphenol;
(f) 20 to 35% by weight of a water-soluble salt filler;
(g) 2.5 to 10% by weight of a dye;
(h) optionally, up to 5% by weight of a cationic quaternary ammonium salt;
(i) optionally, up to 10% by weight of a perfume;
and (j) 4 to 15% by weight of a plasticizer.
In order that the invention may be better understood the following Examples are given by way of illustration only. In the Examples, all parts and percentages are by weight unless otherwise stated.
The following Examples are for compositions suited for forming shaped bodies of blocks by a casting/moulding operation.
EXAMPLE I
Distea~ate Dissolution Test To determine the dissolution rate of polyethylene glycol distearate in water the test is performed as follows:
A sample of the polyethylene glycol distearate is placed into a beaker and heated so as to form a melt.
Using a 7.5 ml capacity polyethylene transfer pipet, one drop of the melt is placed in the centre of a petri dish.
.
13 ~332~3~
The drop is allowed to fully solidify for ten minutes, then 75 ml of deionized water is added to the dish. The dish is monitored to determine the time xequired for the drop of surfactant to totally dissolve.
A dissolution time of at least about 5.5 hours indicates that the polyethylene glycol distearate with the desired molecular weight i8 suitable for use in formiulating the composition of the invention.
E~AMPLE II
A. Procedure for the Selection of PolyethYlene Glycol 6000 Distearate (PEG 6000DS~
To determine the dissolution rate of polyethylene glycol distearate in water the test is performed as follows:
1. An aliquot of PEG 6000DS is placed in a beaker and melted.
2. Using a 7.5 ml polyethylene transfer pipet, a drop of the melt i8 transferred to a microscope glass slide, the weight of PEG
6000DS added being 0.02 ~ or -OoOOl g using an analytical balance. The melt is allowed to solidify for ten minutes.
TOILET BOWL CLEANER
The present invention relates to cake compositions which are useful for the treatment of the flush water of toilets. More particularly, the invention i5 concerned with a long lasting toilet tank dispenser which may be formed by casting and is responsive to the flushing of the toilet.
This application is a divisional of copending Canadian patent application Serial No. 540,143 filed June 19, 1987.
In treating toilet flush water with chemicals in order to produce desirable effects such as bowl aesthetics, cleaning, disinfection, deodorization, aerosol reduction, etc., it is desirable that the 15 che~icals be dispensed into the flush water automatically each time the toilet i8 flushed. The prior art discloses numerou~ devices which have been designed for this purpose.
Particularly desirable devices are those comprising 20 a solid cake composition. In this type of device, a measured amount of water enters the device during one flush cycle and remains in contact with the cake between flushes, thereby forming a concentrated solution of the composition which i8 dispensed into the flush water ~` 25 during the next flush. The advantages of such devices are that the chemical composition can be packaged and shipped in more concentrated form than aqueous solutions of the chemicals. Also, the problems of liquid spillage resulting from breakage of the dispensers during shipment 30 or handling is eliminated.
s Prior art surfactant cake compositions are disclosed in U.S. 4,308,625 (Kitko) and U.S. 4,043,931 (Jeffrey et al). These patents disclose a lavatory cleansing tablet which is formed with two or more non-ionic surfactants 35 which incIudes the use of polyalkoxylated alcohols.
-` ~33233~
U.S. 4,477,363 (Wong et al) discloses a solid cake comprising free fatty alcohol and a buffered alkali earth metal alkyl sulfate surfactant.
JP 58-168699 (Japan Synthetic Rubber Co. et al) discloses a cast lavatory cleansing block containing 25 to 90 weight % of a mixtuxe of polyethylene glycol or monoester thereof and polyethylene glycol diester. The preferred monoester and diester are the stearates and the exemplified stearates are polyethylene glycol 4000 and 6000 monostearates and polyethylene glycol 6000 distearate. The block may also contain inter alia a deodorizing agent, detergent, colorant, filler, binder, aromatic, and dissolution rate adjuster.
JP 58-25398 (Lion) discloses a cast lavatory cleansing block containing 40 to 98 weight % of polyethylene glycol diester, preferably distearate.
Especially preferred diesters are polyethylene glycol 1500, 3000 and 9000 distearates. The block may also contain inter alia aromatic, colorant, surface-active agent, ger~icide, and builder.
JP 59-24797 (Earth I) discloses a cast lavatory cleansing block containing at least 40~ of a polyethylene glycol distearate having 91 to 230 moles ethylene oxide adduct groups and 0.1 to 60% of either polyoxyethylene sorbitan monositearate, 6 ethylene oxide or polyethylene sorbitan tristearate, 20 ethylene oxide. Exemplified polyethylene glycol distearates have 91, 160, 230 and 245 moles ethylene oxide. The block may also contain inter alia dye and fragrance.
JP 61-83300 (Earth II) discloses a cast lavatory cleansing block containing 1-8 volume % 12-hydroxy stearic acid and/or 0.1-5% benzylidene sorbitol, 20-70%
perfume; 10-30% coloring matter; and 15-60% surface active agent. The surface active agent can comprise a polyethylene glycol distearate. The block may also contain inter alia deodorant, bactericide and chlorine-remover.
~ .
~ v~
3 ~33233~
u.s. 4,269,723 (sarford et al I) discl~ses a compressed lavatory cleansing block containing one or i~
more organic surface active agents and one or more binders which binder(s) act as dissolution retarding agents and are selected from clays and water-soluble and water-dispersible gel-forming organic polymeric materials. Specified binders include alginates and carragheenates and specified surface active agents include alkylene oxide condensates of fatty acids.
G.B. 2,061,g96 A (Jeyes) is substantially the same as Barford et al I except that the block is formed by melting lower-melting point components, dispersing higher melting point and/or liquid components in the melt, and then casting into a mould.
U.s. 4,460,490 (Barford et al II) discloses a bi-component lavatory cleansing block comprising a shaped body formed of a slow-dissolving cleansing composition containing at least one surface active agent and a tablet comprising a bleaching agent embedded in or adhered to the shaped body. The shaped body preferably comprises one or more readily-soluble surface active agents in admixture with one or more solubility control agents.
Specified solubility control agents include low ethoxylates of fatty acids and gel-forming gums, such as xanthan gum, or materials, such as alginates or - carragheenates.
U.S. 4,310,434 (Choy et al) and U.S. 4,278,571, (Choy) disclose surfactant cake compositions containing ~; dyes and perfumes which are utilized in the present invention. The surfactants provide cleaning and sudsing in the toilet bowl and also serve to dispense other components of the compositions such as dyes, perfumes, organic resins, etc.
Water-soluble inert salts such as alkali metal chlorides and sulfates are used in such compositions to act as a "filler" so that the composition can be formed ,: :
~ A
.`~ .
4 ~ 3 ~
into cakes of desirable size without using excessive amounts of active ingredients. The predominant ingredients of the cake compositions are usually the surfactant, perfume and the filler salt.
A major problem in this art has been short and/or erratic longevity of surfactant cakes because of rapid and uneven dissolution resulting in decreased cake stability and longevity.
It has been found that a cast solid cake composition which has a long and uniform block life can be provided where the composition comprises a polyethylene glycol distearate if said distearate has a specific water solubility and molecular weight range.
The present invention is directed towards the provision of a solid cake which may be formed by casting and comprises a specific kind of polyethylene glycol distearate, which compositions are suitable for use for automatically dispensing cleansing agent~ into the toilet, particularly a cast solid cake composition having relatively high melt temperatures and less block surface tackine6s for improved processing.
The present invention is further directed towards the provision of a lavatory block which has a long and uniform block life that eliminates sluggish toilets and which resists mounding and major fragmentation.
In accordance with the present invention, there is provided a solid cake lavatory cleansing block composition, which comprises (i) about 8 to about 35% by weight of the composition of a polyethylene glycol distearate having a drop dissolution time of at least about 5.5 hours according to the Distearate Dissolution Test (see Example 1 hereinafter) and a molecular weight from about 3,000 to 12,000, preferably about 7,000 to 9,000, (ii) about 20 to about 64% by weight of the composition of a water-soluble salt filler, and (iii) up to about 40% by weight of the composition of a non-ionic surfactant. Optional ingredients are selected from the j"
~`` 5 133233~
groups consisting of fragrances, dyes, binders, filler materials and mixtures thereof. As noted above, the cake composition comprises from about 8% to about 35%, preferably about 12% to 29%, by weight of said polyethylene glycol distearate. It is known that polyethylene glycol distearate is extremely hydrophilic.
Because of the extreme hydrophilic nature of the compound, it would be expected that the material would be very water soluble without any prolonged transition from solid to a liquid. It has been surprisingly found that the particular kind of polyethylene glycol distearate of the invention goes through a hydration stage forming a tenacious gel so as to provide the aforementioned extended block life relative to other formulations containing polyethylene glycol distearate of varying molecular weights.
It is critical in the present invention that the polyethylene glycol distearate which is utilized in the formulation of the cake composition has a drop dissolution time of at least about 5.5 hours according to the Distearate Dissolution Test. It has been found that not all polyethylene glycol distearates having a molecular weight of about 3,000 to 12,000 possesses such a characteristic. Their method of preparation appears to influence their solubility. Preferably, their ~ preparation is according to the method of condensing a ^~ fatty acid with an alcohol as described by W.B. Satkowski ; et al in HPolyoxyethylene esters of Fatty Acids", ionic Surfactants M.J. Schick Ed. (Dekker, ~Y 1967) p.
142-17A. For example, stearic acid having a molecular weight of 284.5 is reacted with a polyethylene glycol having a molecuIar weight range between 5500-8500 to form a polyethylene glycol distearate having a molecular weight range of about 6033-9033. Such compound having a dissolution time of at least 5.5 hours is suitable for use in the invention.
.~
, :, .~
~332336 In order to improve the cake characteristics, it has been found advantageous to utilize in the cake composition a greater portion of polyethylene glycol distearate which has a molecular weight betwe0n about 7,000 to about 12,000. A lesser portion of polyethylene glycol distearate having a molecular weight between about 3,000 to about 7,000, preferably about 3,000 to about 4,000 in combination with the higher molecular weight polyethylene glycol distearate aids in preventing mounding and further acts as a binder.
The compositions of the invention also comprise a non-ionic surfactant. Non-ionic surfactants that may be included are the condensation products of a long chain ethylene oxide moiety with an aliphatic alcohol, preferably a primary or secondary aliphatic alcohol, or an alkyl phenol. Preferably the primary and secondary alcohol contains 8 to 20 carbon atoms and the alkyl phenol-based moiety is one wherein the alkyl chain is straight or branched and contains 6 to 12 carbon atoms, 2~ preferably 6 to 9 carbon atoms.
Illustrative non-ionic surfactants having the desired characteristics for foxmulation are available on the market under the Trade Marks "Neodol" (Shell Oil Co~pany); "Tergitol" (Union Carbide Company); and "Alfol"
(Continental Oil Company). Specific examples include "Neodol 25-7" (linear C12-C15 primary alcohol condensed with 7 moles of ethylene oxide per mole of alcohol);
"Neodol 45-7" (linear C14-C15 primary alcohol condensed with 7 moles of ethylene oxide per mole of alcohol);
"Tergitol 15-S-7" (random secondary C11-C15 alcohol condensed with 7 moles of ethylene oxide per mole of alcohol); and "Alfol 1416-6.5" (primary C14-Cl6 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol).
Such non-ionic surfactants act as coupling agents to provide an integration of the cake components and may be :
~,,; ~ ~ , ~ t3323~
used in the amount of up to about 40%, preferably about 20 to about 30%, by weight of the cake formulation.
Also useful to enhance the life of the cake are ethoxylated nonylphenols. The high ethoxylated nonylphenols, that is those having over 20 moles of ethylene oxide per mole of phenol, provide slow dissolution of the cake formulation. Up to about 10%, preferably up to 5~, by weight of ethoxylated nonylphenols is prePerably utilized together with the ethoxylated aliphatic alcohols.
Water-soluble inert salts are used in the present compositions as "fillers" so that the composition can be formed into cakes of desired size without using excessive amounts of active ingredients. They are used alone or in combination in amounts up to about 64% by weight.
The inert salts (filler salts) used in the compositions of the present invention can be any water-soluble inorganic or organic salt or mixtures of such salts. For purposes of the present invention, "water-soluble" means having a solubility in water of at least 0.2 grams per hundred qrams of water at 20C. Examples of suitable salts include various alkali metal and/or alkaline earth metal sulfates, chlorides, borates, bromides, citrates, acetates, lactates, etc.
Specific examples of suitable salts include calcium sulfate, sodium chloride, potassium sulfate, sodium carbonate, lithium chloride, tripotassium phosphate, sodium borate, potassium bromide, potassium fluoride, sodium bicarbonate, calcium chloride magnesium chloride, sodium citrate, sodium acetate, calcium lactate, .~ j .
magnesium sulfate and sodium fluoride. The preferred salts are the inorganic salts, especially the alkali metal sulfates and chlorides. Particularly preferred salts, because of their low cost, are calcium sulfate and sodium chloride. The salts are present in the compositions herein at levels of from about 20% to about ~ ~ 64% by weight, preferably from about 20% to about 35%.
"~
: ` ~
~33~
Most preferably, sodium chloride i6 utilized togetherwith guar gum (binder) either alone or with other salts since the combination not only provides a synergistic viscosity increase of water and decreases the relative solubility properties of the matrix in water but also aids to prevent mounding.
Calcium sulfate is advantageously utilized alone or together with other natural gum binders or together with sodium chloride because it has a low solubility level which is constant over the water temperature range likely to exist within toilet tanks.
It has been found that natural gums can advantageously be utilized as binders in the present invention. The natural gums ~hich may be utilized are those which arc cold water gelling additives and develop a high viscosity and a high gel strength. Included in the gums which may be utilized are guar, xanthan, tragacanth, carrageenan, karaya, algin, and the like.
Usually, the gum i8 present in an amount of 3 to 35%, preferably 5 to 15%, by weight of the composition. The most preferable is guar which has been found to be the most effective in retarding block dissolution and to reduce the problem of sluggish toilet behaviour.
As mentioned above, it has been found to be particularly advantageous to utilize guar gun, together with sodium chloride as a filler since there is a synergistic viscosity increase of water that is not found with other fillers such as calcium sulfate.
Additionally, there is an increase of the relative 3Q insolubility properties of the matrix in water.
As a further binding agent, the use of solid emollients have been found to be helpful to prevent the cake of the invention from mounding out. Suitable ~; emollients include glyceryl monostearate, glyceryl monopalmitate, ethylene glycol stearate, propylene glycol monostearate, and the like, most preferably is glyceryl monostearate whiGh provides a matrix to prevent mounding.
.
l ~~
:
11 332~3~
The emollients may be utilized in amounts of up to about 20% by weight, pre~erably about 5% to about 12%.
Variou~ optional materials may be included in the compositions herein.
Dyes may be included at levels of up to 15%, preferably about 2.5% to 10% by weight. Examples of suitable dyes are Alizarine Light Blue B (C.I. 63010), Carta 81ue VP (C.I. 24401), Acid Green 2G (C.I. 42085), Astragon Green D (C.I. 42040), Supranol Cyanine 7B (C.I.
10 42675), Maxilon Blue 3RL (C.I. Basic Blue 80), Drimarine Blue Z-RL (C.I. Reactive Blue 18), Alizarine Light Blue H-RL (C.I. Acid Blue 182), FD&C Blue No. 1, FD&C Green No.3 and Acid Blue No. 9 (C.I. 42090). Others are disclosed in the aforementioned Patent Nos. 4,310,434 and 15 4,477,363.
The cakes of the invention may also contain up to about 15% by weight of a cationic quaternary ammonium salt.
It is known that the cationic quaternary ammonium salts which include a greater number of short-chain alkyl groups in the structure, incline toward better bacteriostatic properties. Speci~ic examples of bacteriostatic agents that may be used in the compositions of this invention include di-isobutyl cresoxy ethoxy ethyl dimethyl benzyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, myristyl dimethylbenzene ammonium chloride, benzalkonium chloride, cetyl pyridinium chloride, coconut dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl diethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium bromide, di-isobutyl phenoxy ethoxy ethyl trimethyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl alkyl ammonium chloride, methyl-dodecylbenzyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, octadecyl dimethyl ethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide, ; ' : ~
-~ 13~23~
octadecenyl-9-dimethyl ethyl ammonium bromide, dioctyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, hexadecynyl trimethyl ammonium iodide, octyltrimethyl ammonium fluoride, and mixtures thereof. Other water dispersible salts, such as the acetates, sulfates, nitrates, and phosphates, are effective in place of the halides, but the chlorides and bromides are preferred.
The cakes may also contain perfumes to impart an acceptable odor to the flushing water. The perfume may be in solid form and is suitably present in an amount up to 15%, preferably up to 10%, by weight. In this connection, it may be noted that the term "perfume" is intended to refer to any material giving an acceptable odor and thus materials giving a "disinfectant" odor such as essential oils, pine extracts, terpinolenes, ortho phenyl phenol or paradichlorobenzene may be employed.
The essential oils and pine extracts also contribute as plasticizers and are functional to a degree in extending block life.
Certain perfume materials may be added which additionally function to control the solubility of anionic sulfate surfactants. Examples of such perfume materials are isobornyl acetate myrtenyl acetate and frenchyl acetate. Other suitable perfume or fragrances are diæclosed in U.S. Patent No. 4,396,522 of Callicott et al.
The cake formulation may also contain other binding and/or plasticizing ingredients serving to assist in the i manufacture thereof, for example, polypropylene glycol having a molecular weight from about 3,000 to about 10,000 in an amount up to about 20% by weight preferably about 4% to about 15% by weight of the mixture may be used. The polypropylene glycol reduces the melt ~; viscosity, acts as a demolding agent and also acts to plasticize the block when the composition is prepared by ',!
.
~'` .
}~" -~ 33233~
a casting process. Other suitable plasticizers such as pine oil fractions, d-limonene, dipentene and the ethylene oxide-propylene oxide block copolymers may be utilized.
The blocks of the present invention can be produced by a variety of processes, e.g., casting/moulding process, by tablet compression process or by an extrusion process. The casting process being the prefèrred process of the invention.
The casting process which is well within the skill of those in the art involves the melting of the ingredients and then casting the melt into appropriate shaped moulds and allowing the mel~ to cool and solidify.
The shaped tablets or blocks each suitably have a weight of from 20 to 150 grams, preferably from 30 to 70 grams.
In one preferred embodiment, the compositions of the invention comprise from 8 to 35% by weight of the polyethylene glycol distearate; up to 40% by weight of the non-ionic surfactant; up to 64% by weight of water-so}uble salt filler; and at least one of:
(a) up to 35% by weight of a gelling natural gum;
(b~ up to 20% by weight of a solid emollient binding agent;
(c) up to 10% by weight of an ethoxylated nonylphenol;
(d) up to 15% by weight of a dye;
(e) up to 15% by weight of a cationic quaternary ammonium salt;
(f) up to 15% by weight of a perfume; and (g~ up to 20% by weight of a plasticizer.
In one especially preferred embodiment, said preferred compositions comprise 20 to 30% by weight of an ethoxylated C8-C20 aliphatic alcohol, up to 32% by weight -~
of sodium chloride and/or up to 32% by weight of calcium - sulfate, from 4% to 15% by weight of plasticizer, and at -~
l-ast one of~
up to 10% by weight of glyceryl monostearate; ~-~
up to 10% by weight of ethoxylated nonylphenol;
12 ~l 3 ~
up to 35% by weight of guar gum; and up to 15% of disinfecting agents, coloring and/or fragrances.
In another especially preferred embodiment, said preferred composition comprises:
(a) from 12 to 29% by weight of the polyethylene glycol distearate;
(b) 5 to 15% by weight of a gelling natural gum;
(c) 5 to 12% by weight of a solid emollient binding agent;
(d) 20 to 30% by weight of a non-ionic surfactant;
(e) optionally, up to 10% by weight of an ethoxylated nonylphenol;
(f) 20 to 35% by weight of a water-soluble salt filler;
(g) 2.5 to 10% by weight of a dye;
(h) optionally, up to 5% by weight of a cationic quaternary ammonium salt;
(i) optionally, up to 10% by weight of a perfume;
and (j) 4 to 15% by weight of a plasticizer.
In order that the invention may be better understood the following Examples are given by way of illustration only. In the Examples, all parts and percentages are by weight unless otherwise stated.
The following Examples are for compositions suited for forming shaped bodies of blocks by a casting/moulding operation.
EXAMPLE I
Distea~ate Dissolution Test To determine the dissolution rate of polyethylene glycol distearate in water the test is performed as follows:
A sample of the polyethylene glycol distearate is placed into a beaker and heated so as to form a melt.
Using a 7.5 ml capacity polyethylene transfer pipet, one drop of the melt is placed in the centre of a petri dish.
.
13 ~332~3~
The drop is allowed to fully solidify for ten minutes, then 75 ml of deionized water is added to the dish. The dish is monitored to determine the time xequired for the drop of surfactant to totally dissolve.
A dissolution time of at least about 5.5 hours indicates that the polyethylene glycol distearate with the desired molecular weight i8 suitable for use in formiulating the composition of the invention.
E~AMPLE II
A. Procedure for the Selection of PolyethYlene Glycol 6000 Distearate (PEG 6000DS~
To determine the dissolution rate of polyethylene glycol distearate in water the test is performed as follows:
1. An aliquot of PEG 6000DS is placed in a beaker and melted.
2. Using a 7.5 ml polyethylene transfer pipet, a drop of the melt i8 transferred to a microscope glass slide, the weight of PEG
6000DS added being 0.02 ~ or -OoOOl g using an analytical balance. The melt is allowed to solidify for ten minutes.
3. The glass slide i8 carefully placed in a 1000 ml glass beaker containing 800 cc deionized water which is immersed in a 38-C water bath.
4. The beaker is monitored to determine the time necessary for the drop of PEG 6000DS to totally dissolve. A dissolution time of at least 5.5 hours indicated that the polyethylene glycol distearate was suitable for use in formulating the composition of the invention.
B. Preparatio~ of Cake Composition Polyethylene glycol 6000 distearate from Part A 21%
Ethoxylated C~2-C15 Linear, Primary Alcohol with 7E0 29.5 14 ~3233~
Ethoxylated Nonylphenol with 100 EO5.5%
Ethylene oxide-propylene oxide block copolymer (8500 MM 80% EO) 3.5%
Acid Blue No.9 dye 5.5%
~ipentene 8.0%
Ortho-phenyl phenol 1.0%
Guar gum 5.5%
Sodium chloride 20.5%
Into a first mixture vessel four-fifths of the ethoxylated C12 - C~5 linear primary alcohol is added and slowly heated with stirring. The polyethylene glycol 6000 distearate, ethoxylated nonylphenol and ethylene oxide-propylene oxide block copolymer are added and the mixture is heated with stirring to 71~C to form a clear melt.
In a separate vessel, to the remaininq one-fifth of the ethoxylated linear primary alcohol there is added with stirring the dye, the dipentene and the ortho-phenyl phenol. The mixture i5 then added to the first mixing vessel followed by the guar gum and the sodium chloride.
The mixture is cooled to 57C and poured into molds.
After cooling to 5C, the blocks are removed from the mold.
EXAMPLE III
Following the procedure of Example II, a shaped lavatory cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate9.0%
Glyceryl monostearate 5.5%
30 Ethoxylated C12-C15 Linear, Primary Alcohol with 7EO 20.0%
Ethoxylated Ceto Stearyl Alcohol with 50 EO 17.5%
Acid Blue No.9 dye 5.5~
35 Terpinolene 8.0%
;~ Ortho-phenyl phenol 1.0%
::
.... ~ . ~ ~ .. .. .. . .. .... . .. .. . ..
~332336 Guar gum 9.5%
Sodium chloride 24.0%
EXAMPLE IV
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate20.0%
Glyceryl monostearate - acid stable10.0%
Ethoxylated aliphatic alcohol (Neodol 45-7) 20.0%
Guar gum 9.0%
Sodium chloride 26.0%
Polypropylene glycol (PPGDI000) 5.0%
Cetyl trimethy~ ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0%
Terpinolene 5.0%
The composition had a melt viscosity of 2000 cps (2 Pa.s) at 49-C and a set point at 46-C. The shaped tablet had an in-tank life of more than 30 days and showed only ~` slight mounding.
EXAMPLE V
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients~
Polyethylene glycol 6000 distearate20.0%
Glyceryl monostearate - acid stable10.0%
Ethoxylated aliphatic alcohol ~; (Neodol 45-7) 21.0%
Guar gum 6.0%
Sodium chloride 26.0%
Polypropylene glycol (PPGD1000) 6.0%
30, Cetyl trimethyl ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0%
`~: : ::
Terpinolene 6.0%
The composition had a melt viscosity of 1120 cps (1-~ 2 Pa.s) at 51C and a set point at 46C. The shaped ; 35 tablet had an in-tank life of 20-40 days in 6 different ~; ~ toilets and mounded out after 30 days. ~`
16 ~L33233~
EXAMPLE VI
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate16.5%
Glyceryl monostearate - acid stable5.5%
Ethoxylated aliphatic alcohol (N~odol 45-7) 25.0%
Guar gum 6.0% ~:-Sodium chloride 32.0%
Polypropylene glycol (PPGD1000) 5.0%
Cetyl trimethyl ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0~
Terpinolene 5.0%
The shaped co~position had an in-tank life of about 30 days and showed only slight flattening.
EXAMPLE VII
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients: :
Polyethylene glycol 6000 distearate12.5~
Glyceryl monostearate - acid stable5.5%
Ethoxylated aliphatic alcohol (Neodol 45-7) 23.0%
Ethoxylated nonylphenol (NP100) 4.0%
Guar gum 8.0%
Sodium chloride 32.0%
: Polypropylene glycol (PPGD1000) 5.0%
- Cetyl trimethyl ammon~um bromide 1.0%
~ Acid Blue No. 9 dye 4.0%
.j 30 Terpinolene . 5.0%
The shaped composition had an in-tank life of about -: 25-30 days in 6 different toilets and showed only slight ~:~ mounding.
EXAMPLE VIII
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
; Polyethylene glycol 6000 distearate 16.5%
t~
:
17 ~ 3323~ -Glyceryl mono~tearate 5 5%
Ethoxylated aliphatic alcohol (Neodol 45-7) 23.0%
Calcium sulfate 32.0%
B. Preparatio~ of Cake Composition Polyethylene glycol 6000 distearate from Part A 21%
Ethoxylated C~2-C15 Linear, Primary Alcohol with 7E0 29.5 14 ~3233~
Ethoxylated Nonylphenol with 100 EO5.5%
Ethylene oxide-propylene oxide block copolymer (8500 MM 80% EO) 3.5%
Acid Blue No.9 dye 5.5%
~ipentene 8.0%
Ortho-phenyl phenol 1.0%
Guar gum 5.5%
Sodium chloride 20.5%
Into a first mixture vessel four-fifths of the ethoxylated C12 - C~5 linear primary alcohol is added and slowly heated with stirring. The polyethylene glycol 6000 distearate, ethoxylated nonylphenol and ethylene oxide-propylene oxide block copolymer are added and the mixture is heated with stirring to 71~C to form a clear melt.
In a separate vessel, to the remaininq one-fifth of the ethoxylated linear primary alcohol there is added with stirring the dye, the dipentene and the ortho-phenyl phenol. The mixture i5 then added to the first mixing vessel followed by the guar gum and the sodium chloride.
The mixture is cooled to 57C and poured into molds.
After cooling to 5C, the blocks are removed from the mold.
EXAMPLE III
Following the procedure of Example II, a shaped lavatory cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate9.0%
Glyceryl monostearate 5.5%
30 Ethoxylated C12-C15 Linear, Primary Alcohol with 7EO 20.0%
Ethoxylated Ceto Stearyl Alcohol with 50 EO 17.5%
Acid Blue No.9 dye 5.5~
35 Terpinolene 8.0%
;~ Ortho-phenyl phenol 1.0%
::
.... ~ . ~ ~ .. .. .. . .. .... . .. .. . ..
~332336 Guar gum 9.5%
Sodium chloride 24.0%
EXAMPLE IV
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate20.0%
Glyceryl monostearate - acid stable10.0%
Ethoxylated aliphatic alcohol (Neodol 45-7) 20.0%
Guar gum 9.0%
Sodium chloride 26.0%
Polypropylene glycol (PPGDI000) 5.0%
Cetyl trimethy~ ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0%
Terpinolene 5.0%
The composition had a melt viscosity of 2000 cps (2 Pa.s) at 49-C and a set point at 46-C. The shaped tablet had an in-tank life of more than 30 days and showed only ~` slight mounding.
EXAMPLE V
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients~
Polyethylene glycol 6000 distearate20.0%
Glyceryl monostearate - acid stable10.0%
Ethoxylated aliphatic alcohol ~; (Neodol 45-7) 21.0%
Guar gum 6.0%
Sodium chloride 26.0%
Polypropylene glycol (PPGD1000) 6.0%
30, Cetyl trimethyl ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0%
`~: : ::
Terpinolene 6.0%
The composition had a melt viscosity of 1120 cps (1-~ 2 Pa.s) at 51C and a set point at 46C. The shaped ; 35 tablet had an in-tank life of 20-40 days in 6 different ~; ~ toilets and mounded out after 30 days. ~`
16 ~L33233~
EXAMPLE VI
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate16.5%
Glyceryl monostearate - acid stable5.5%
Ethoxylated aliphatic alcohol (N~odol 45-7) 25.0%
Guar gum 6.0% ~:-Sodium chloride 32.0%
Polypropylene glycol (PPGD1000) 5.0%
Cetyl trimethyl ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0~
Terpinolene 5.0%
The shaped co~position had an in-tank life of about 30 days and showed only slight flattening.
EXAMPLE VII
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients: :
Polyethylene glycol 6000 distearate12.5~
Glyceryl monostearate - acid stable5.5%
Ethoxylated aliphatic alcohol (Neodol 45-7) 23.0%
Ethoxylated nonylphenol (NP100) 4.0%
Guar gum 8.0%
Sodium chloride 32.0%
: Polypropylene glycol (PPGD1000) 5.0%
- Cetyl trimethyl ammon~um bromide 1.0%
~ Acid Blue No. 9 dye 4.0%
.j 30 Terpinolene . 5.0%
The shaped composition had an in-tank life of about -: 25-30 days in 6 different toilets and showed only slight ~:~ mounding.
EXAMPLE VIII
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
; Polyethylene glycol 6000 distearate 16.5%
t~
:
17 ~ 3323~ -Glyceryl mono~tearate 5 5%
Ethoxylated aliphatic alcohol (Neodol 45-7) 23.0%
Calcium sulfate 32.0%
5 Guar gum 8.0%
Polypropylene glycol (PPGDlO00) 5.0%
Cetyl trimethyl ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0%
Terpinolene 5.0%
10 The shaped tablet mounded out after 30 days in-tank.
In lieu of guar gum, an equal amount of any one of the aforementioned natural gums may be utilized.
EXAMPLE IX
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients~
Polyethylene glycol 6000 distearate 30.0 Glyceryl monostearate 20.0 Ethoxylated ceto stearyl alcohol with 50E0 20.0%
20 Acid Blue No. 9 dye 4.0%
Cetyl trimethyl ammonium bromide 1.0%
Calcium sulfate 25.0%
The resulting block had the following characteristics:
Demolding Drop Out Block surface Dry Specific gravity 1.11 EXAMPLE X
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate 20.0%
Glyceryl monostearate 15.0%
Ethoxylated ceto stearyl alcohol with 50E0 20.0%
35 Ethoxylated aliphatic alcohol (Neodol 25-7) 5.0%
Acid Blue No. 9 dye 4.0%
18 ~33233~
Cetyl trimethyl ammonium bromide 0.9%
Polypropylene glycol 425 10.0%
Calcium sulfate 20.1%
Terpinolene 5.0%
The resulting block had the following characteristics:
Demolding Light Tap Block surface Dry In-tank life (days) 30 Mounding Slight Mounding EXAMPLE XI
Following the procedure of Exa~ple II, a shaped cake composition is prepared with the following ingredient~:
Polyethylene glycol 6000 distearate20.0%
Glyceryl monostearate 10.0%
Ethoxylated ceto stearyl alcohol with 50E0 20.0%
Ethoxylated aliphatic alcohol (Neodol 25-7) 5.0%
Acid Blue No. 9 dye 4.0%
Cetyl trimethyl ammonium bromide 0.9%
Polypropylene glycol 425 10.0%
Calcium sulfate 25.1~
Terpinolene 5.0%
The resulting block had the following characteristics:
Demolding Drop Out Block surface Dry Specific gravity 1.19 Mounding Slight Mounding i , EXAMPLE XII
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate 20.0%
Glyceryl monostearate 12.0%
Ethoxylated ceto stearyl alcohol with 50E0 20.0%
13~33~
Ethoxylated aliphatic alcohol (Neodol 25-7) 6.0%
Acid Blue No. 9 dye 4.0%
Cetyl trimethyl ammonium bromide o.9%
Polypropylene glycol 425 9.o%
Calcium sulfate 23.1% :
Terpinolene 5.0%
The resulting block had the following characteristics: :
10 Demolding Drop Out Block surface Dry Specific qravity 1.21 ~:
In-tank life (days) 27 -~ounding None -~
EXAMPLE XIII ~:
Following the procedure of Example II, a shaped cake :~
composition is prepared with the following ingredients~
Polyethylene glycol 6000 distearate22.5 Glyceryl monostearate 10.0%
20 Ethoxylated ceto stearyl alcohol with 50E0 17.5%
Ethoxylated aliphatic alcohol (Neodol 25-7) 5.0%
Acid Blue No. 9 dye 4.0%
25 Cetyl trimethyl a onium bromide 0.5%
Polypropylene glycol 425 10.0%
Calcium sulfate 25.5%
Terpinolene 5.0~
: The resulting block had the following : 30 characteristics:
Demolding Light Tap Block surface Dry Specific gravity 1.24 In-tank life (days) 8 toilets, : 35 20-26 days Mounding None ~ ' ' . .
/
133233~
EXAMPL~_XIV
PROCEDURE FQR PRELIMINARY EVALUATION OF THE NOUNDING
AND COUPLING PROPERTIES OF A TOILET BLOCK
To determiine the potential for a block to (1) mound or spread out from its original shape; and (2) remain an integrated unit once the block has been immersed in water, a test is conducted as follows:
1. Two 2000 ~1 glass beakers are filled with tap water. One is placed in a refrigerator at about 5C for ait least four hours while the other beaker remains at ambient temperature.
2. One block from the sample lot is placed in each beaker. The blocks remain im~ersed in water overnight or about sixteen hours.
3. The block are then observed after the immersion period. The a~bient temperature sample provides an indication of the degree of spreading or enlarging of the block base that may occur during immersion within a toilet tank. The 5C sample provides an indication of the integration of the block components or tendency to dissolve in unison.
The principals, preferred embodiments and modes of operation of the pre~ent invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the scope of the invention as defined in the following claims.
.. . .
.
Polypropylene glycol (PPGDlO00) 5.0%
Cetyl trimethyl ammonium bromide 1.0%
Acid Blue No. 9 dye 4.0%
Terpinolene 5.0%
10 The shaped tablet mounded out after 30 days in-tank.
In lieu of guar gum, an equal amount of any one of the aforementioned natural gums may be utilized.
EXAMPLE IX
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients~
Polyethylene glycol 6000 distearate 30.0 Glyceryl monostearate 20.0 Ethoxylated ceto stearyl alcohol with 50E0 20.0%
20 Acid Blue No. 9 dye 4.0%
Cetyl trimethyl ammonium bromide 1.0%
Calcium sulfate 25.0%
The resulting block had the following characteristics:
Demolding Drop Out Block surface Dry Specific gravity 1.11 EXAMPLE X
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate 20.0%
Glyceryl monostearate 15.0%
Ethoxylated ceto stearyl alcohol with 50E0 20.0%
35 Ethoxylated aliphatic alcohol (Neodol 25-7) 5.0%
Acid Blue No. 9 dye 4.0%
18 ~33233~
Cetyl trimethyl ammonium bromide 0.9%
Polypropylene glycol 425 10.0%
Calcium sulfate 20.1%
Terpinolene 5.0%
The resulting block had the following characteristics:
Demolding Light Tap Block surface Dry In-tank life (days) 30 Mounding Slight Mounding EXAMPLE XI
Following the procedure of Exa~ple II, a shaped cake composition is prepared with the following ingredient~:
Polyethylene glycol 6000 distearate20.0%
Glyceryl monostearate 10.0%
Ethoxylated ceto stearyl alcohol with 50E0 20.0%
Ethoxylated aliphatic alcohol (Neodol 25-7) 5.0%
Acid Blue No. 9 dye 4.0%
Cetyl trimethyl ammonium bromide 0.9%
Polypropylene glycol 425 10.0%
Calcium sulfate 25.1~
Terpinolene 5.0%
The resulting block had the following characteristics:
Demolding Drop Out Block surface Dry Specific gravity 1.19 Mounding Slight Mounding i , EXAMPLE XII
Following the procedure of Example II, a shaped cake composition is prepared with the following ingredients:
Polyethylene glycol 6000 distearate 20.0%
Glyceryl monostearate 12.0%
Ethoxylated ceto stearyl alcohol with 50E0 20.0%
13~33~
Ethoxylated aliphatic alcohol (Neodol 25-7) 6.0%
Acid Blue No. 9 dye 4.0%
Cetyl trimethyl ammonium bromide o.9%
Polypropylene glycol 425 9.o%
Calcium sulfate 23.1% :
Terpinolene 5.0%
The resulting block had the following characteristics: :
10 Demolding Drop Out Block surface Dry Specific qravity 1.21 ~:
In-tank life (days) 27 -~ounding None -~
EXAMPLE XIII ~:
Following the procedure of Example II, a shaped cake :~
composition is prepared with the following ingredients~
Polyethylene glycol 6000 distearate22.5 Glyceryl monostearate 10.0%
20 Ethoxylated ceto stearyl alcohol with 50E0 17.5%
Ethoxylated aliphatic alcohol (Neodol 25-7) 5.0%
Acid Blue No. 9 dye 4.0%
25 Cetyl trimethyl a onium bromide 0.5%
Polypropylene glycol 425 10.0%
Calcium sulfate 25.5%
Terpinolene 5.0~
: The resulting block had the following : 30 characteristics:
Demolding Light Tap Block surface Dry Specific gravity 1.24 In-tank life (days) 8 toilets, : 35 20-26 days Mounding None ~ ' ' . .
/
133233~
EXAMPL~_XIV
PROCEDURE FQR PRELIMINARY EVALUATION OF THE NOUNDING
AND COUPLING PROPERTIES OF A TOILET BLOCK
To determiine the potential for a block to (1) mound or spread out from its original shape; and (2) remain an integrated unit once the block has been immersed in water, a test is conducted as follows:
1. Two 2000 ~1 glass beakers are filled with tap water. One is placed in a refrigerator at about 5C for ait least four hours while the other beaker remains at ambient temperature.
2. One block from the sample lot is placed in each beaker. The blocks remain im~ersed in water overnight or about sixteen hours.
3. The block are then observed after the immersion period. The a~bient temperature sample provides an indication of the degree of spreading or enlarging of the block base that may occur during immersion within a toilet tank. The 5C sample provides an indication of the integration of the block components or tendency to dissolve in unison.
The principals, preferred embodiments and modes of operation of the pre~ent invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the scope of the invention as defined in the following claims.
.. . .
.
Claims (16)
1. A solid cake lavatory cleansing block composition comprising:
(i) about 8 to about 35% by weight of the composition of polyethylene glycol distearate having a molecular weight from 3,000 to 12,000 and a drop dissolution time (time for a fully solidified melt phase drop dispensed from a 7.5 ml pipette to completely dissolve in 75 ml deionized water at ambient temperature) of at least about 5.5 hours, (ii) about 20 to about 64% by weight of the composition of a water-soluble salt filler, and (iii) up to about 40% by weight of the composition of a non-ionic surfactant.
(i) about 8 to about 35% by weight of the composition of polyethylene glycol distearate having a molecular weight from 3,000 to 12,000 and a drop dissolution time (time for a fully solidified melt phase drop dispensed from a 7.5 ml pipette to completely dissolve in 75 ml deionized water at ambient temperature) of at least about 5.5 hours, (ii) about 20 to about 64% by weight of the composition of a water-soluble salt filler, and (iii) up to about 40% by weight of the composition of a non-ionic surfactant.
2. A cleansing block composition as claimed in claim 1 or claim 2, wherein said polyethylene glycol distearate comprises a mixture of a major proportion of polyethylene glycol distearate having a molecular weight between about 7,000 and about 12,000 and a minor proportion of polyethylene glycol distearate having a molecular weight between about 3,000 and about 7,000.
3. A cleansing block composition as claimed in claim 1, wherein said non-ionic surfactant is selected from ethoxylated aliphatic (C8-C20) alcohols and ethoxylated C6-C12 alkyl phenols.
4. A cleansing block composition as claimed in claim 1,wherein the amount of said non-ionic surfactant is about 20 to about 30% by weight.
5. A cleansing block composition as claimed in claim 1, including a mixture of ethoxylated nonylphenols having more than 20 moles of ethylene oxide per mole of phenol.
6. A cleansing block composition as claimed in claim 5, wherein said ethoxylated nonylphenols are present in an amount up to about 10% by weight.
7. A cleansing block composition as claimed in claim 1 wherein said water-soluble salt filler is an alkali metal or alkaline earth metal chloride or sulfate.
8. A cleansing block composition as claimed in claim 7, wherein said filler is sodium chloride or calcium sulphate.
9. A cleansing block composition as claimed in claim 1 including a gelling natural gum selected from guar, xanthan, tragacanth, carrageenan, karaya and algin.
10. A cleansing block composition as claimed in claim 1, including a binding agent selected carom glyceryl monostearate, glyceryl monopalmitate, ethylene glycol stearate, and propylene glycol monostearate.
11. A cleansing block composition as claimed in claim 1, including a cationic quaternary ammonium salt.
12. A cleansing block composition as claimed in claim 1, including a plasticizer selected from polypropylene glycol, dipentene, pine oil fractions, d-limonene and ethylene oxide-propylene oxide copolymers.
13. A cleansing block composition as claimed in claim 1 further comprising, based on percent by weight of the composition, of at least one component selected from the group consisting of:
(a) up to 35% by weight of a gelling natural gum, (b) up to 20% by weight of a solid emollient binding agent;
(c) up to 10% by weight of an ethoxylated nonylphenol;
(d) up to 15% by weight of a dye;
(e) up to 15% by weight of a cationic quaternary ammonium salt;
(f) up to 15% by weight of a perfume; and (g) up to 20% by weight of a plasticizer.
(a) up to 35% by weight of a gelling natural gum, (b) up to 20% by weight of a solid emollient binding agent;
(c) up to 10% by weight of an ethoxylated nonylphenol;
(d) up to 15% by weight of a dye;
(e) up to 15% by weight of a cationic quaternary ammonium salt;
(f) up to 15% by weight of a perfume; and (g) up to 20% by weight of a plasticizer.
14. A cleansing block composition as claimed in claim 13, comprising:
(a) from 12 to 29% by weight of said polyethylene glycol distearate;
(b) 5 to 15% by weight of a gelling natural gum;
(c) 5 to 12% by weight of a solid emollient binding agent;
(d) 20 to 30% by weight of a non-ionic surfactant:
(e) 20 to 35% by weight of a water-soluble salt filler;
(f) 2.5 to 10% by weight of a dye; and (g) 4 to 15% by weight of a plasticizer.
(a) from 12 to 29% by weight of said polyethylene glycol distearate;
(b) 5 to 15% by weight of a gelling natural gum;
(c) 5 to 12% by weight of a solid emollient binding agent;
(d) 20 to 30% by weight of a non-ionic surfactant:
(e) 20 to 35% by weight of a water-soluble salt filler;
(f) 2.5 to 10% by weight of a dye; and (g) 4 to 15% by weight of a plasticizer.
15. A cleansing composition as claimed in claim 14 further comprising at least one component selected from the group consisting of;
(a) up to 10% by weight of the composition of an ethoxylated nonylphenyl:
(b) up to 5% by weight of a cationic quaternary ammonium salt; and (c) up to 10% by weight of a perfume.
(a) up to 10% by weight of the composition of an ethoxylated nonylphenyl:
(b) up to 5% by weight of a cationic quaternary ammonium salt; and (c) up to 10% by weight of a perfume.
16. A cleansing block composition as claimed in claim 1 comprising from 8% to 35% by weight of said polyethylene glycol distearate; up to 30% by weight of ethoxylated aliphatic (C8-C20) alcohol; up to 32% by weight of sodium chloride: and/or up to 32% by weight of calcium sulfate;
and from 4% to 15% by weight of plasticizer; and at least one of:
(i) up to 10% by weight of glyceryl monostearate;
(ii) up to 10% by weight of ethoxylated nonylphenol;
(iii) up to 35% by weight of guar gum; and (iv) up to 15% by weight of disinfecting agent, coloring and/or fragrance.
and from 4% to 15% by weight of plasticizer; and at least one of:
(i) up to 10% by weight of glyceryl monostearate;
(ii) up to 10% by weight of ethoxylated nonylphenol;
(iii) up to 35% by weight of guar gum; and (iv) up to 15% by weight of disinfecting agent, coloring and/or fragrance.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US876,923 | 1986-06-20 | ||
US06/876,923 US4722801A (en) | 1986-06-20 | 1986-06-20 | Toilet bowl cleaner in cake form containing a polyethyleneglycol distearate |
CA000540143A CA1322139C (en) | 1986-06-20 | 1987-06-19 | Toilet bowl cleaner |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000540143A Division CA1322139C (en) | 1986-06-20 | 1987-06-19 | Toilet bowl cleaner |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1332336C true CA1332336C (en) | 1994-10-11 |
Family
ID=25671386
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000616543A Expired - Fee Related CA1332336C (en) | 1986-06-20 | 1993-01-11 | Toilet bowl cleaner |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA1332336C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115279878A (en) * | 2020-03-13 | 2022-11-01 | 联合利华知识产权控股有限公司 | Cleaning composition |
-
1993
- 1993-01-11 CA CA000616543A patent/CA1332336C/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115279878A (en) * | 2020-03-13 | 2022-11-01 | 联合利华知识产权控股有限公司 | Cleaning composition |
CN115279878B (en) * | 2020-03-13 | 2024-07-26 | 联合利华知识产权控股有限公司 | Cleaning composition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0369992B1 (en) | Toilet bowl cleaner | |
US4911858A (en) | Toilet bowl cleaner | |
EP2121893B1 (en) | Self-sticking disintegrating block for toilet or urinal | |
AU2008238106B2 (en) | Self adhesive hard surface cleaning composition | |
EP0423391B1 (en) | Toilet bowl cleaners containing iodophors | |
CA2071017A1 (en) | Lavatory cleansing and sanitizing blocks | |
US5449473A (en) | Lavatory cleansing and sanitizing blocks containing a halogen release bleach and a polybutene stabilizer | |
US5342550A (en) | Solid delivery systems for toilet tanks, urinals and condensate water | |
US4438015A (en) | Lavatory cleansing block | |
AU2008238138A1 (en) | Toilet cleaning block | |
CA1332336C (en) | Toilet bowl cleaner | |
US4780236A (en) | Lavoratory cleansing block containing polyethylene gycol disteatrate, guar gum and sodium chloride | |
IE60827B1 (en) | Toilet bowl cleaner | |
CN1183463A (en) | Long-acting bactericidal sterilizing descaling deodorizing composition for toilet bowl, and preparing process thereof | |
CA2001187C (en) | Toilet bowl cleaner | |
NZ231142A (en) | Solid block composition containing guar gum and polyethylene oxide homopolymers for use in treating flush water in toilets | |
JPH0816239B2 (en) | Deodorant antifouling agent for flush toilets | |
CA2001186C (en) | Toilet bowl cleaners containing iodophors | |
EP0051891A1 (en) | Improved polyethylene oxide cake with reduced gelling for flush toilet wastewater sanitation | |
NZ231141A (en) | Solid block composition containing ioduphors and polyethylene oxide polymer for use in treating flush water in toilets |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKLA | Lapsed |