Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/645—Mixtures of compounds all of which are cationic
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/044—Hydroxides or bases
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/362—Phosphates or phosphites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/34—Derivatives of acids of phosphorus
  • C11D1/345—Phosphates or phosphites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/42—Amino alcohols or amino ethers
  • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• This invention relates to improvements in the art of cleaning objects, particularly those made of metal, glass, etc.
• the invention pertain to detergents composed of alkaline builders and surfactants.
• An object of the invention is to provide a means for solubilizing polyethylene oxide non-ionic surfactants into builder solutions.
• a further object is to provide homogeneous built liquid detergents and alkaline cleaners containing polyethylene oxide non-ionic and alkaline builders.
• Alkaline cleaners are the most widely used means in industry for cleaning metal, glass, certain plastics, etc. In the metal-forming field, in particular, such cleaners are used to remove various types of soil such as cutting oils, grinding, buifing, stamping, and drawing compounds.
• the alkaline cleaning solution may be used for soaking, spraying, or electrolyti types of cleaning. Of these, the soaking or tank cleaning technique is most important because of its widespread use in industry.
• the article to be cleaned usually is dipped in or slowly transported through a hot alkaline solution with little or no agitation present.
• the cleaning solutions employed generally are made up of materials consisting of between about 88 and 99 percent by weight of various alkalies, such as caustic soda, sodium metasilicate, sodium orthosilicate, soda ash, trisodium phosphate (TSP), tetrasodium pyrophosphate (TSPP), and tetrapotassium pyrophosphate (TKPP), and from about 1 to 12 percent by weight to a surfactant.
• TSP trisodium phosphate
• TSPP tetrasodium pyrophosphate
• TKPP tetrapotassium pyrophosphate
• the concentration of the cleaning materials (alkali plus surfactant) in the tank or bath is maintained between 0.5 and percent of the cleaning solution.
• the cleaning baths will contain from 0.005% to 1.2% surfactant and 0.5 to 10.0% of the alkaline builders.
• the surfactant employed is not thoroughly soluble in the hot alkaline solution, it will tend to oil out oraccumulate at the surface of the bath. There are a number of reasons why this is undesirable and why it is important to have the alkali and surfactant homogeneously dispersed throughout the bath.
• One objection is the fact that a layer of surfactant on the surface will tend to adhere to and thereby contaminate the otherwise cleaned object as it is withdrawn from the bath, and the thus-contaminated surfaces Will be difiicult to clean by the normal rinsing operations which follow.
• nonionics One of the best-known and effective surfactants for metal cleaning and the like is the class known as nonionics. Particularly effective members of this class are the polyethylene oxide type non-ionics, such as Triton X- 100. However, the use of such non-ionics in hot cleaning solutions containing alkaline builders has the disadvantage that they are not completely soluble in such baths.
• Triton X-lOO would be far above its cloud point in hot 5% caustic or mixed alkaline builders. This would cause the non-ionic to oil out on top of the bath.
• Triton X becomes completely and readily soluble and effective in the alkaline solution.
• compositions of the solubilizers or hydrotropes which are useful in the present invention are surfaceactive materials which contain upwards of 85% primary phosphate esters (i.e., monoester phosphate) components.
• esters are members of the class consisting of the condensation product, and the salts of said condensation product, of the reaction of polyphosphoric acid and a compound having the formula R(CH CH O) H.
• R must be either an alkyl phenoxy group, the alkyl radical of which is in the range of C to C or an alkoxy group, the alkyl radical of which is in the range of C C and x is a number from 1 to 20.
• novel phosphate ester hydrotropes are prepared by a process disclosed in copending application Serial No. 255,173 (now U.S. Patent 3,235,627, issued February 15, 1966), which was filed on January 31,1963, by Richard C. Mansfield. (That application, incidentally, is a continuation-in-part of Serial No. 195,952, which was filed on May 18, 1962, and since abandoned.)
• the contents of the specifications of both those applications are incorporated herein by reference for purposes of expanding upon the present disclosure, even though some of the products disclosed therein may not be useful in the present invention.
• the said esters are prepared by reacting from about 0.6 mol to about 2.0 mols of polyphosphoric acid with 1.0 mol of a condensation product having the formula R(CH CH O) H as indicated above.
• the polyphosphoric acid which is used is a mixture of phosphoric acids with a phosphoric acid anhydride content corresponding to about 73 to 85 percent expressed as P.
• the effectiveness of the above hydrotropes in solubilizing non-ionic surfactants can readily be demonstrated by comparing them with a number of prior art solubilizers such as sodium xylene v sulfonate, et al.
• alkyl or alkylphenoxy polyethylene oxide phosphate compositions of the present invention thus to solubilize non-ionic surfactants, such as Triton X-100, in builder solutions applies to such hydrotropes in which the ethylene oxide content varies from about 1 to about 20 units. Within this range, a very minimum amount of the hydrotrope effectively solubilizes the nonionic in hot alkaline metal cleaning baths and in built liquid detergents. This is illustrated in Table II where two systems are compared, as follows:
• Either of these two systems can be used as a standard for accepting or rejecting hydrotropes which are desired for solubilizing non-ionic surfactants. It has been determined that in either of these systems a ratio of 1.5 parts of solubilizer per part of Triton X-100 is the practical upper limit. That is, to be suitable as a solubilizer for non-ionic surfactants in builder solutions, no more than 1.5 parts of the hydrotrope must be required to solubilize Triton X100. Any more than that would be uneconomical and wasteful so as not to be commercially acceptable.
• any hydrotrope may be compared to determine whether it will be suitable for solubilizing non-ionic surfactants.
• Table II shows a comparison of hydrotropes, including those of the present invention, functioning to solubilize Triton X- 100 under each of the two systems described above. It will be seen that only hydrotropes of the present invention required less than 1.5 parts thereof for each part of Triton X-100. By comparison, all the other hydrotropes listed required considerably higher quantities to accomplish the same result.
• E ethylene oxide.
• 0PEx octylphenoxy ethylene oxide (with x units of ethylene oxide)
• Product (1) is e phosphated non ionic surfactant prepared by the reaction of an ootylpheonoxy(polyethoxy)m ethanol and P205 by the procedure described in U.S. Patent 3,001,056.
• Product (2) is identical with product (1) except that the number of polyethoxy units is 11.5.
• Nos. 16 and 17 are blends like those disclosed in U.S. Patent 3,004,056.
• No. 16 consists of 80% primary phosphate terminated and 20% unreacted non-ionics.
• No. 17 consists of 80% primary phosphate terminated and 20% secondary phosphate.
• Triton X-lOO alone among the numerous polyethoxy non-ionic surfactants has been cited to illustrate its relative insolubility in hot alkaline solutions or in builder solutions. However, it should be understood that this condition is quite general for substantially all polyethoxy non-ionic surfactants. This is illustrated in Table III below.
• OPEX octylphenoxy ethylene oxide (with 1 units of ethylene oxide).
• N PEx nonylphenoxy ethylene oxide (with x units of ethylene oxide).
• iSolubilizer used OPE PO Hg. Ratio of solubilizer to non-ionic Norns:
• the alkyl portion of the alkylphenoxy compounds can range from about C to C
• the alkyl portion of the alkylamine compounds can range from about C to C (Examples 11 and 12 in the table illustrating mixtures of C C
• the alkyl portion of the alkoxy compounds can also range from about C to C (Example 10 illustrating a C compound which is mid-way in that range).
• OTESZ (1) Bath run at 82 C., using 0.25% surfactant, and 5.0% base (NaOH/ Na2CO3/Na2SiO3 at ratios of 40/28.5/3l.5). (2) Octylphenoxy ethylene oxide; phosphate and Triton X-lOO in a 1:1 ratio, along with 5% of same base and other bath conditions specified in note (1) above.
• compositions of the present invention are exceptionally useful in making it possible to utilize the superior non-ionic surfactants,,of the alkoxy, alkylamine and alkylphenoxy polyoxyethylene type, in various built alkaline detergent solutions and in hot alkaline cleaning baths.
• non-ionic surfactants such as Triton X-l00.
• Such surfactants tend to lose their normally high cleaning efiiciency in the presl Brightstock oil (Sun 150), min., 82 0., 5.0% base (NaOH/Na COS Na SiO3 at ratios 40/28.5/31.5).
• the addition of the solubilizer of the present invention has prevented a loss in cleaning efficiency of the non-ionic surfactant which otherwise would be caused by a high soil load.
• the solubilization of the surfactant by the addition of the inventive composition reduces its tendency to adsorb on solid or dissolve in the oily phase, either or both being probable causes for the decrease in the surfactants cleaning efliciency when forced to function under heavy soil conditions.
• One such use is in a textile processing operation known as open boil, whose purpose is to remove sizing or dressing agents and/or natural waxes and oils from cotton.
• the cotton is boiled for a specified period, e.g., 30 minutes, in a bath containing 0.05% surfactant and 6.0% NaOH.
• the boiled samples are then rinsed in warm running Water, hydroextracted, pressed dry, and conditioned overnight at 70 F. and 65% relative humidity.
• the present invention makes possible superior wetting action in a caustic solution 'at ambient temperatures as might be used in a desizing operation on cotton fabrics.
• Draves test 5 gram skein, 3 gram hook
• octylphenoxypolyoxyethylene (with 9.7 units of ethylene oxide)
• the surfactant was above the cloud point here.
• octylphenoxypolyoxyethylene phosphate with 7.5 units of ethylene oxide at 0.2% concentration and used in a 2.0% NaOH solution at 90 C., had such poor wetting action that it was useless in a bleaching operation where it was desired to have the caustic solution wet or penetrate a certain fabric.
• a liquid detergent concentrate is prepared by mixing together 0.5% of a blend of non-ionic and hydrotrope therefor with an alkaline builder and water, as follows:
• the concentrate is a clear, non-separating, homogeneous liquid in temperatures from to 50 C. It is useful in cleaning floor waxes from vinyl tile at concentrations of about 1.5% in water.
• Example 2 A liquid detergent concentnate is prepared by mixing together 20.0% of a blend of non-ionic and hydrotrope therefor with an alkaline builder and water, as follows:
• the concentrate is a clear, non-separating, homogeneous liquid in temperatures from 0 to 50 C. It contains approximately 20% surfactant and 45% total solids. It is useful in cleaning metallic brown soil from linoleum at concentrations of about 1.0% detergent in water.
• Example 3 A liquid detergent concentrate is prepared by mixing together 0.5% of a blend of non-ionic and hydrotrope therefor with 4.0% of alkaline builder and water, as follows:
• the concentrate is a clear, non-separating, homogeneous liquid in temperatures from 0 to 50 C. It is useful in cleaning soil from walls.
• Example 4 A liquid detergent concentrate is prepared by mixing together 10.0% of a blend of non-ionic and hydrotrope therefor with 10.5% of alkaline builders and water, as follows:
• the concentrate is a clear, non-separating, homogeneous liquid in temperatures from 0 to 50 C. It is useful for cleaning mineral oils from painted substrates and linoleum.
• Example 5 An alkaline cleaning bath is prepared by mixing together 0.005% of a blend of non-ionic and hydrotrope therefor with 0.5 of alkaline builders and water, as follows:
• the bath is a clear, non-separating, homogeneous liquid in temperatures from 0 to C. It is useful in hot solutions for removing mineral oils from steel.
• Example 6 An alkaline cleaning bath is prepared by mixing together 0.50% of a blend of non-ionic and hydrotrope therefor with 10.0% of alkaline builders and water, as follows:
• the bath is a clear, non-separating, homogeneous liquid in temperatures from 0 to 100 C. It is useful in hot solutions for removing paint from steel.
• Example 7 An alkaline cleaning bath is prepared by mixing together 0.08% of a blend of non-ionic and hydrotrope therefor with 4.9% of alkaline builders and water, as follows:
• the bath is a clear, non-separating, homogeneous liquid in temperatures from 0 to 100 C. It is useful in hot solutions for removing mineral oils from steel.
• Example 8 A composition useful for preparing alkaline cleaning baths is prepared by mixing together 0.50% of 'a blend of non-ionic and hydrotrope therefor with 99.5% alkaline builders and water, as follows:
• a bath When dissolved at a concentration of 5% in hot water, a bath is formed which is clear, non-separating and homogeneous. The bath is effective in removing mineral oils from steel.
• Example 9 A composition useful for preparing alkaline cleaning baths is prepared by mixing together 25% of a blend of non-ionic and hydrotrope therefor with 75% alkaline builders and water, as follows:
• a bath When dissolved at a concentration of 2% in hot water, a bath is formed which is clear, non-separating and homogeneous. The bath is effective in removing mineral oils from steel.
• compositions of the present invention are wide in their scope, both with regard to their formulation and their use, and are not necessarily limited by the examples hereinabove disclosed.
• a composition which is useful in alkaline cleaning solutions and in liquid detergent concentrates essentially consisting of: from about 75 to about 99.5 percent of an alkaline builder from the class consisting of the sodium and potassium hydroxides, carbonates, silicatesand phosphates, and from about 25 to about 0.5 percent of a blend of about 10 to about 80 percent of a nonionic surfactant and from about 90 to about 20 percent of a hydrotrope therefor, said non-ionic 'being a member of the class consisting of alkoxy, alkylamine and alkylphenoxy polyethoxy adducts having from 1 to about 30 units of ethylene oxide, the alkyl portion of the alkoxy compounds having 10 to 15 carbon atoms, the alkyl portion of the alkylamine compounds having 10 to 15 carbon atoms, and the alkyl portion of the alkylphenoxy compounds having 8 to 12 carbon atoms, and said hydrotrope being a surface-active composition, which contains upwards of 85% primary phosphate esters
• An alkaline cleaning bath essentially consisting of: water and an alkaline builder from the class consisting of the sodium and potassium hydroxides, carbonates, silicates and phosphates, and a blend of about 10 to about 80 percent of a non-ionic surfactant and about 90 to 20 percent of a hydrotrope therefor, said non-ionic being a member of the class consisting of alkoxy, alkylamine and alkylphenoxy polyethoxy adducts having from 1 to about 30 units of ethylene oxide, the alkyl portion of the alkoxy compounds having 10 to carbon atoms, the alkyl portion of the alkylamine compounds having 10 to 15 carbon atoms, and the alkyl portion of the alkylphenoxy compounds having 8 to 12 carbon atoms, and said hydrotrope being a surface-active composition, which contains upwards of 85% primary phosphate esters, of the class consisting of the condensation product and the salts of said condensation product of the reaction of polyphosphoric acid and a compound having the formula
• a liquid detergent concentrate comprising: water, an alkaline builder from the class consisting of the sodium and potassium hydroxides, carbonates, silicates and phosphates, and a blend of about 10 to about 80 percent of a non-ionic surfactant and about 90 to 20 percent of a hydrotrope therefor, said non-ionic being a memher of the class consisting of alkoxy, alkylamine and alkylphenoxy polyethoxy adducts having from 1 to about 30 units of ethylene oxide, the alkyl portion of the alkoxy compounds having 10 to 15 carbon atoms, the alkyl portion of the alkylamine compounds having 10 to 15 carbon atoms, and the alkyl portion of the alkylphenoxy compounds having 8 to 12 carbon atoms, and said hydrotrope being a surface-active composition, which contains upwards of primary phosphate esters, of the class consisting of the condensation product and the salts of said condensation product of the reaction of polyphosphoric acid and a compound having the formula R (CH
• composition of claim 13 The composition of claim 1 in which the alkyl group in the nonionic alkyl phenoxy polyethoxy adduct is octyl.
• composition of claim 1 in which the alkyl group in the nonionic alkyl phenoxy polyethoxy adduct is nonyl.
• composition of claim 15 in which the alkyl group in the nonionic alkoxy polyethoxy adduct is tridecyl.

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Cited By (18)

Citations (10)

• 0
  • BE BE632444D patent/BE632444A/xx unknown
  • NL NL292944D patent/NL292944A/xx unknown
  • IT IT700621D patent/IT700621A/it unknown
• 1963
  • 1963-05-15 DE DER35185A patent/DE1243313B/de active Pending
  • 1963-05-16 GB GB19512/63A patent/GB1016081A/en not_active Expired
  • 1963-05-17 FR FR935275A patent/FR1365398A/fr not_active Expired
  • 1963-05-17 AU AU30827/63A patent/AU288953B2/en not_active Expired
• 1965
  • 1965-03-12 US US439472A patent/US3294693A/en not_active Expired - Lifetime

Patent Citations (10)

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