GB1599036A

GB1599036A - Liquid textile-treatment composition

Info

Publication number: GB1599036A
Application number: GB2273877A
Authority: GB
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1977-05-30
Filing date: 1977-05-30
Publication date: 1981-09-30
Also published as: FR2393099A2; FR2393099B2

Description

(54) LIQUID TEXTILE-TREATMENT COMPOSITION (71) We, THE PROCTER & GAMBLE COMPANY, a company organised under the laws of the State of Ohio, of 301 East Sixth Street, Cincinnati, Ohio 45002, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to fabric softening compositions and, in particular, to the compositions in the form of an aqueous emulsion or dispersion. The present invention is an improvement in or a modification of the invention claimed in our co-pending British patent application No. 29103/76, (Specification Serial No. 1,550,205), hereinafter termed the "parent invention".

Textile treatments with a view to providing desirable fabric characteristics in addition to textile cleaning, have found wide-spread application by both the textile industry and housewives. Such textile-treatment technology can be carried out in conjunction with the laundry cleaning operation or, as is perhaps most frequently the case, subsequent to the laundry cleaning operation. It aims at conferring on the fabric a series of desirable handling benefits inclusive of fabric softness, smoothness, pliability, fluffiness, static cling control and ease-of-ironing. Among those benefits fabric softening has acquired special standing and textile softening compositions are sold mostly for use by housewives.These compositions usually contain as a fabric substantive agent a cationic compound containing a quaternary ammonium derivative having at least two long alkyl chains, for example distearyl dimethyl ammonium chloride. The positive charge of the softening compound facilitates its deposition onto the fabric substrate, the surface of which is usually negatively charged.

However, although the above mentioned cationic compounds can be effective softeners when applied from a rinse solution, there are certain disadvantages associated with their use. For example, the cationic compounds having long alkyl chains are very sensitive to carry over of anionic detergent into the rinse. Thus, carry-over of anionic detergent tends to neutralize the softening effect because the anionic-cationic complex tends to precipitate out of solution. Also, certain cationic surfactant compounds are expensive and it is therefore desirable, for commericial reasons, to provide softening compositions having a reduced amount of cationic surfactant compound.Furthermore, softening compositions which comprise predominantly long chain cationic compounds have the disadvantage that the treated fabrics tend to become overloaded with softener and become discolored. greasy or undesirably non-absorbent.

Certain nonionic compounds have been proposed for use in fabric softening agents.

Because of the delicate balancing required to provide acceptable storage stability, it became necessary to provide additional nonionic softening aids which can be effectively utilized with a very broad range of textile softeners under various usage conditions inclusive of from a rinsing operation.

Some of the individual components of the compositions of the present invention are raw materials which have found application in the textile-treatment industry in general. For example, Germany patent application DOS 20 04 721, published on October 7, 1971 relates to softening compositions for washed textiles containing a di-long chain alkyl substituted bis-quaternay ammonium compound and optionally nonionic capillary-active emulsifying agents. Preferred emulsifying agents include polyethers derived from fatty alcohols with a relatively high number of ether groups. It is mentioned that other conventional rinse-softener ingredients can be added in the usual quantities.Germany patent application 20 09 722, published on September 30, 1976 relates to the use of di-long chain alkyl substituted bisquarternary ammonium compounds in textile cleaning compositions containing in addition to the bis-quarternary compound, conventional detergent surfactants, detergent builders and other usual additives for the like compositions. German patent application DAS 14 19 362, published on January 23, 1969, relates to textile softening compositions containing a conventional softener ingredient in combination with an additive which projects against anionic components. The protective additive can be represented by ethoxyatedtertiary amines and ethoxylated di-tertiary amines.

German patent application DOS 26 22 104, published on December 2, 1976 relates to liquid rinse softener compositions containing a diamine antistatic agent and a quarternary ammonium textile softener. German patent application DOS 26 31 114, published on February 10, 1977 pertains to rinse softener compositions containing a polyamine salt and a specific nonionic fabric conditioning substance.

It is an object of the present invention to provide liquid rinse-softening compositions which employ specific nonionic fabric lubricants and substituted polyamines, the salts or partial salts thereof, which compositions provide excellent deposition onto the fabric surface from aqueous solution.

This and other objects are achieved by means of a composition which is disclosed in more detail in the following.

Summary of the invention The present invention is based on the discovery that the deposition of specific nonionic fabric lubricants onto fabrics can be markedly increased if they are combined with certain cationic polyamine compounds. It appears that, when the appropriate nonionic fabric lubricant and the appropriate cationic compounds are emulsified together, emulsion particles are formed which have a suitable positive charge for good deposition onto fabrics to occur.

The compositions herein described comprising a substituted polyamine and a nonionic fabric lubricant are capable of providing outstanding textile benefits from a rinse-softening operation. More specifically the liquid treatment composition herein described comprises: (a) from 0.5% to 12% by weight of a substituted polyamine salt or a partial salt, having the formula

wherein R is an alkyl or alkenyl group having from 12 to 22 carbon atoms in the alk(enyl chain, the R1 's which may be the same or different each represent hydrogen atom or a -(C2H4O)pH or -(C3H6O)gH, or a C13 alkyl group. where each of p and g may be 0 or a number such that( p+g) does not exceed 15, m is an integer from 1 to 5 and n is an integer from 2 to 6, R2 is R or R1 with the proviso that no more than one of the R2,s is R, and in the salt or partial salt form A(-) represents one or more anions having a total charge balancing that of the nitrogen atom; (b) from 0.5% to 12% by weight of a nonionic fabric lubricant selected from: : i. the esters of fatty alcohols having from 12 to 24 carbon atoms and mono- or polycarboxylic acids having from 1 to 8 carbon atoms, whereby the total number of carbon atoms in the ester is equal to or greater than 16; ii. mono-ethers of fatty alcohols having from 10 to 24 carbon atoms and mono- or poly-alochols having from 2 to 8 carbon atoms, whereby the total number of carbon atoms in the ether is equal to or greater than 16; iii. compounds of the formula R3 - X - R4 wherein R3 is a hydrocarbyl radical which has from 12 to 24 carbon atoms and R4 is a hydrocarbyl radical which has from 1 to 6 carbon atoms which can be hydroxyl-substituted and can be interrupted by not more than one oxygen link, and X stands for sulfur,

and (c) a liquid carrier.

In a preferred aspect, the compositions herein additionally comprise up to about 6% by weight of a cationic compatibilizing agent selected from di-C10-C22 alkyl, di-Cl to C4 alkyl ammonium compounds: C8 C25 alkyl imidazolinium salts and mixtures thereof.

Detailed description of the invention The compositions of the present invention comprise a substituted polyamine salt (or partial salt), a nonionic fabric lubricant and optionally a conventional softening component, and preferably water. These individual components are described in more detail hereinafter.

Unless specified to the contrary, the "percent" indications stand for percent by weight.

The esential substituted polyamine component can be represented by the formula:

wherein R is an alkyl or alkenyl group having from 12 to 22 carbon atoms in the alk(en)yl chain, the Rl's which may be the same or different each represent hydrogen or a -(C2H4O)pH or -(C3H6O)gH, or a C13 alkyl group, where each of p and g may be 0 or a number such that (p+g) does not exceed 15, m is an integer from 1 to 5, preferably 1 or 2, and n is an integer from 2 to 6, R2 is R or R1 with the proviso that no more than one of the R21s, is R, and in the salt or partial salt from A- represents one or more anions having a total charge balancing that of the nitrogen atoms.

Polyamine species suitable for use herein include: N-tallowyl ,N N' N' -tris(2-hydroxyethyl) 1 3-propanediamine di-hydrochloride; Nsoybean alkyl-1,3-propane diammonium sulfate; N-stearyl-N-N'-di(2-hydroxyethyl)-N'-(3-hydroxypropyl)-1,3-propanediamine dihydrof- luoride; N-cocoyl N,N,N',N' ,N'-pentamethyl-l ,3-propane diammonium dichloride; N-oleyl N,N' ,N'-tris(3-hydroxypropyl)- 1,3-propanediamine dihydrofluoride; N-stearyl N,N'-N'-tris(2-hydroxyethyl) N,N' -dimethyl-1 ,3-propanediammonium dimethylsulfate; N-palmityl N,N',N'-tris(3-hydroxypropyl)-1,3-propanediamine dihydrobromide.

Preferred polyamine species herein have from about 16 to 18 carbon atoms in the alkyl chain.

It is recognized that polyalkylene oxide species can be attached to nitrogen atoms. The alkoxylating radical can thus be represented by polyoxythylene, a polyoxypropylene or a mixed polyoxyethylene/oxypropylene radical.

Preferred species frequently contain an ethylene oxide or propylene oxide radical condensed on one or more of the nitrogen atoms of the polyamine. The most preferred species contain one ethylene oxide or one propylene oxide group directly condensed onto each nitrogen atom.

may may represent atom a di-halide or any appropriate acidic radical such as a di-acetate, or higher saturated or unsaturated carboxylic acid groups up to C22, and more in general all nitrogen charge on balancing anions which are known to be suitable for use in these compositions. Preferred nitrogen charge balancing anions can be represented by halides, Cl 22 alkyl-, Cl-Cl6 alkyl-aryl- or arylsulf(on)ates, or arylcarboxylates and C1-C12 alkylcarboxylates. Examples of the preferred charge balancing anions include : fluoride, bromide, chloride, methyl sulfate, toluene-, xylene-, cumene-, and benzene- sulfonate, dodecylbenzenesulfonate, benzoate, parahydroxybenzoate, acetate, propionate and laurate.

The polyamines are used in an amount from 0.5 to 12%, preferably from 1 to 8% and more preferably from 2 to 6% of the liquid textile-treatment composition. Using less than about 0.5% of the above polyamines will no longer provide the overall textile benefits provided by the claimed compositions.

A second essential component for use in the compositions herein described is represented by a nonionic fabric lubricant selected from: i. the esters of fatty alcohols having from 12 to 24 carbon atoms and mono- or polycarboxylic acids having from 1 to 8 carbon atoms, whereby the total number of carbon atoms in the ester is equal to or greater than 16; ii. mono-ethers of fatty alcohols having from 10 to 24 carbon atoms in the alkyl chain and mono- or poly-alcohols having from 2 to 8 carbon atoms, whereby the total number of carbon atoms in the ether is equal to or greater than 16;; iii. compounds of the formula R3-X-R4 wherein R3 is a hydrocarbyl radical which has from 12 to 24 carbon atoms and R4 is a hydrocarbyl radical which has from 1 to 6 carbon atoms which can be hydroxyl-substituted and can be interrupted by not more than one oxygen link and X stands for sulfur,

The fatty alcohol radical in the fatty alcohol esters contains from 12 to 24 carbon atoms.

Examples of suitable fatty alcohols include : stearyl, oleyl, palmityl, lauryl, cocoyl, arachidyl and behenyl alcohol. The fatty alcohol is esterified with a mono- or polycarboxylic acid having from 1 to 8, preferably from 2 to 6 carbon atoms in the alkyl chain.

Examples of suitable monocarboxylic acids include : acetic, propionic, butyric, isobutyric, valeric, lactic, glycolic, and ss,ss'dihydroxy-isobutyric acid. Examples of suitable polycarboxylic acids include : n-butylmalonic, isocitric, citric, malic, maleic and succinic acid.

The total number of carbon atoms in the fatty alcohol esters is equal to or greater than 16.

Specific examples of fatty alcohol esters for use herein include : stearyl acetate, di-palmityl lactate, cocoyl isobutyrate, oleyl maleate, di-oleyl maleate, and tallowyl propionate.

The fatty alcohol radical in the fatty alcohol monoethers can correspond to the fatty alcohol radicals in the ester component described above. Thus suitable fatty alcohols are all those of natural or synthetic origin listed above. The short chain mono- or polyalcohol can contain from 2 to 8 carbon atoms. Examples of suitable species include : ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, sorbitol and pentaerythritol. The total number of carbon atoms in the ether is equal to or greater than 16.

Specific examples of fatty alcohol mono-ethers are represented by : batyl alcohol (stearyl glycerol mono-ether), behenyl ethylene glycol mono-ether, octadecyl vinyl ether, and cocoyl sorbitor mono-ether.

The nonionic fabric lubricant can also be represented by a compound having the formula : R3 - X - R4 wherein R3 has from 12 to 24 carbon atoms and R4 from 1 to 6 carbon atoms in the alkyl chain which can be interrupted by not more than one oxygen link and X stands for sulfur,

Suitable examples of this component include : N-stearyl methacrylamide, stearyl vinyl sulfide, N-palmityl 2-hydroxyethylamide, and N-tallowyl 3-hydroxypropylamide.

The nonionic fabric lubricant is conveniently used in an amount from 0.5% to 12%, preferably from 1% to 8%, and most preferably from 2% to 6%.

The compositions of this invention can optionally contain up to 6% by weight of a cationic compatibilizing agent selected from a conventional water-insoluble quaternary ammonium compound, a C825 alkylimidazolinium salt and mixtures thereof.

Well-known species of substantially water-insoluble quaternary ammonium compounds have the formula:

wherein R12 and R11 represent hydrocarbyl groups of from 10 to 22 carbon atoms; R5 and R6 represent hydrocarbyl groups containing from 1 to 4 carbon atoms; X is an anion, preferably selected from halide and methyl sulfate radicals.Representative examples of quarternary softeners include ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; dihexadecyl dimethyl ammonium bromide; ditallow dipropyl ammonium bromide: di(coconutalkyl) dimethyl ammonium chloride. Ditallow dimethyl ammonium chloride, di(hydrogenated tallow-alkyl) dimethyl ammonium chloride and di(coconut-alkyl) dimethyl ammonium chloride are preferred.

Another class of suitable cationic compatibilizing agents can be represented by C8 25 alkylimidazolinium salts. Preferred salts include those conforming to the formula

wherein Rg is a C1-C4 alkyl radical, R7 is hydrogen or a C1-C6 alkyl radical, R8 is a C8-C25 alkyl radical and Rlo is hydrogen or a C8-Q5 alkyl radical. X is a charge balancing ion which has the same meaning as X defined in the quaternary ammonium compatibilizing agent above.

The optional cationic compatibilizing is frequently used in an amount up to about 6%, preferably in an amount from 0.5% to 4%.

In preferred embodiments of this invention, the weight ratio of substituted polyamine salt (or partial salt) and, if present, cationic compatibilizing agent to nonionic fabric lubricant is equal to or greater than ()0,6, preferably 3 0.9 In addition to the above described components the compositions may contain other textile treatment or conditioning agents. Such agents include silicons, as for example, described in German patent application DOS 26 31 419 incorporated herein by reference.

The optional silicone component can be used in an amount of from about 0.5% to about 6%, preferably from 1% to 4% of the softener composition. In other preferred embodiments of this invention the weight ratio of the sum of nonionic fabric lubricant and silicone to total cationic surfactant is the range from 2:1 to 1:3.

The compositions described herein can contain other ingredients which are known to be suitable for use in textile softeners at the usual concentrations for their known function.

Such adjuvants include emulsifiers, perfumes, preservatives, germicides, viscosity modifiers, colorants, dyes, fungicides, stabilizers, brighteners, and opacifiers. These adjuvants, if used, are normally added at their conventional low levels (eg., from about 0.1% to 5% by weight).

The compositions can normally be prepared by mixing the ingredients together in water, heating to a temperature of about 60"C and agitating for 5-30 minutes.

It is highly preferred and generally provides better performance, first to mix the cationic in the molten nonionic fabric lubricant or to mix both together in liquid form, and then disperse the mixture in the preferably aqueous carrier medium with good agitation.

Depending upon the particular selection of nonionic lubricant and cationic surfactant, it may be necessary in certain cases to include other emulsifying ingredients (eg. common ethoxylated alcohol nonionics) or to employ more efficient means for dispersing and emulsifying the particles (eg. high speed blender).

Normally, at 60 C, the softening agents exist in liquid form and therefore form true emulsions with an aqueous continuous phase. On cooling, the disperse phase may wholly or partially solidify so that the final composition exists as a dispersion which is not a true liquidniquid emulsion. It will be understood that the term "dispersion" means liquid/liquid phase or solid/liquid phase dispersions and emulsions.

For normal use as rinse-added compositions, the disperse phase generally constitutes 1-30%, preferably 3-20% of the softener composition.

The following examples illustrate the invention and facilitate its understanding.

Example 1 A liquid fabric softener composition is prepared by admixing the individual components in a conventional manner.

Ingredients Parts by Weight N-tallowyl-N,N' ,N'-tris(2-hydroxy- ethyl)-1 ,3-propanediamine dihydrochloride 2 Ditallowyl dimethyl ammonium chloride 1.5 Batyl alcohol 3 Water Balance to 100 This composition provides outstanding fabric-softening performance during rinse-softening application.

Substantially identical softening performance is obtained if the diamine component is substituted by an equivalent amount of polyamine selected from: N-soybean alkyl - 1,3-propane diammonium sulfate.

N-cocoyl N, N, N', N', N'-pentamethyl-1,3-propane diammonium dichloride.

N-oleyl N, N', N'-tris(3-hydroxypropyl)-1,3-propanediamine dihydrofluoride.

N-stearyl N, N', N'-tris(2-hydroxyehtyl) N. N'-dimethyl-1,3-propane diammonium dimethylsulfate.

N-palmityl N, N', N'-tris(3-hydroxypropyl)-1 ,3-propane diamine di-hydrobromide.

and mixtures thereof.

Although the compositions herein can be prepared by admixing the components thereby using techniques known per se such as adding separately the individual ingredients under stirring to the water, a preferred manner of preparing the compositions comprises premixing the molten active materials and subsequently dispersing this premix into the water.

Example A series of liquid fabric softener compositions of this invention is prepared by mixing the following ingredients: EXAMPLES (Parts by weight) INGREDIENTS II III IV V VI VII VIII IX N-oleyl-N,N' ,N'-tris(3-hydroxpro pyl)-1 ,3-prnpanediamine dihydrofluo ride 3 2 5 4 N-soybean alkyl- 1 ,3-propane-diammo- nium sulfate 4 3 2 2 Behenyl ethylene glycol mon-ether 3 3 Octadecyl vinyl ether 3 Stearyl acetate 3 N-stearyl methacrylamide 2 5 N-(2-hydroxypropyl)-arachidylamide 3.5 N-palmityl-(2-hydroxyethyl)amide 3.5 Ditallowyl dimethylammonium chloride 1.5 4 1 2 1 1-Methyl-1-tallowyl amidoethyl-2 tallowyl imidazolinium methosulfate 1 2 1 Water and minor additives Balance to 100 These compositions provide fabric benefits at substantially equivalent levels to what is obtained from using under identical conditions the composition of Example I above.

WHAT WE CLAIM IS: 1. A liquid textile treatment composition comprising: (a) from 0.5% to 12% by weight of a substituted polyamine salt or a partial salt, having the formula

wherein R is an alkyl or alkenyl group having from 12 to 22 carbon atoms in the alk(en)yl chain, the Rl's which may be the same or different each represent hydrogen, a (C2H4O)pH or -(C3H6O)gH. or a C13 alkyl group, where each of p and g may be 0 or a number such that (p+g) does not exceed 15, m is an integer from 1 to 5 and n is an integer from 2 to 6, R2 is R or Rl with the proviso that no more than one of the R2,s is R, and in the salt or partial salt form A(-) represents one or more anions having a total charge balancing that of the nitrogen atoms; (b) from 0.5% to 12% by weight of a nonionic fabric lubricant selected from: i. the esters of fatty alcohols having from 12 to 24 carbon atoms and mono- or polycarboxylic acids having from 1 to 8 carbon atoms, whereby the total number of carbon atoms in the ester is equal to or greater than 16; ii. mono-ethers of fatty alcohols having from 10 to 24 carbon atoms and mono- or poly-alcohols having from 2 to 8 carbon atoms; whereby the total number of carbon atoms in the ether is equal to or greater than 16;

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Example A series of liquid fabric softener compositions of this invention is prepared by mixing the following ingredients: EXAMPLES (Parts by weight) INGREDIENTS II III IV V VI VII VIII IX N-oleyl-N,N' ,N'-tris(3-hydroxpro pyl)-1 ,3-prnpanediamine dihydrofluo ride 3 2 5 4 N-soybean alkyl- 1 ,3-propane-diammo- nium sulfate 4 3 2 2 Behenyl ethylene glycol mon-ether 3 3 Octadecyl vinyl ether 3 Stearyl acetate 3 N-stearyl methacrylamide 2 5 N-(2-hydroxypropyl)-arachidylamide 3.5 N-palmityl-(2-hydroxyethyl)amide 3.5 Ditallowyl dimethylammonium chloride 1.5 4 1 2 1

1-Methyl-1-tallowyl amidoethyl-2 tallowyl imidazolinium methosulfate 1 2 1 Water and minor additives Balance to 100 These compositions provide fabric benefits at substantially equivalent levels to what is obtained from using under identical conditions the composition of Example I above.

iii. compounds of the formula R3 - X - R4 wherein R3 is a hydrocarbyl radical which has from 12 to 24 carbon atoms and R4 is a hydrocarbyl radical which has from 1 to 6 carbon atoms which can be hydroxy-substituted and can be interrupted by not more than one oxygen link, and X stands for sulfur,

and (c) a liquid carrier.

2. The composition in accordance with claim 1 wherein the substituted polyamine salt or the partial salt represents from 1% to 8% by weight.

3. The composition in accordance with claim 1 wherein the nonionic fabric lubricant represents from 1% to 8% by weight.

4. The composition in accordance with claim 1 which in addition contains up to 6% by weight of a cationic compatibilizing agent selected: i. a substantially water-insoluble quaternary ammonium compound of the formula

wherein R11 and R12 represent hydrocarbyl groups containing from 10 to 22 carbon atoms, R5 and R6 represent hydrocarbyl groups containing from 1 to 4 carbon atoms, X is an anion; ii. a C8.25 alkyl-imidazolinium salt; and iii. mixtures ktriemciil.azOlinium thereof.

5. The composition in accordance with any of the preceding claims where R in the substituted polyamine has from 16 to 18 carbon atoms and R1 and R2 are derived from ethylene oxide and propylene oxide.

6. The composition in accordance with claim 4 wherein the mono- or polycarboxylic acid in the fatty alcohol ester fabric lubricant has from 2 to 6 carbon atoms in the alkyl chain.

7. The composition in accordance with claim 4 wherein the nonionic fabric lubricant is selected from : N-stearyl methacrylamide, stearyl vinyl sulfide, N-palmityl 2hydroxyethylamide, and N-tallowyl-3-hydroxypropylamide.

8. The composition in accordance with claim 4 wherein the cationic compatibilizing agent is selected from ditallow-dimethylammoniumchloride, di-(hydrogenated tallow) dimethylammonium-chloride and di-(coconut-alkyl) dimethylammoniumchloride.

9. The composition in accordance with claim 4 wherein the polyamine represents from 2% to 6% by weight and is selected from : N-tallowyl,N,N',N' ,-tri-(2-hydroxyethy1)1 ,3- propanediamine dihydrochloride; N-oleyl-N,N' ,N'-tri(3-hydroxypropyl)-1 3- propanediamine dihydrofluoride; N-stearyl-N,N'-bis(2-hydroxyethyl)-N'-(3hydroxypropyl)-1,3 propanediamine dihydrofluoride; and N-palmityl-N,N' ,N'-tris(3hydroxypropyl)-1,3 propanediamine dihydrobromide; the nonionic fabric lubricant represents from 2% to 6% by weight and is selected from: behenyl ethylene-glycol monoether; octadecyl vinylether; N-stearyl methacrylamide; N-(2-hydroxypropyl)-arachidylamide; N-palmityl-(2-hydroxyethyl)amide; stearyl-glycerol-monoether; and octadecylvinylether; and the compatibilizing agent represent from 0.5% to 4% by weight and is selected from: 1-methyl-1-tallowylamidoethyl-2-tallowyl imidazolinium methosulfate, and ditallowdimethyl-ammoniumchloride .

10. A composition in accordance with claim 1 substantially as herein before described in any of the Examples.