Classifications

• • 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
  • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
  • C11D3/485—Halophors, e.g. iodophors
• • 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
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • 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
  • C11D1/825—Mixtures of compounds all of which are non-ionic
  • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/201—Monohydric alcohols linear
  • C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2079—Monocarboxylic acids-salts thereof
• • 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
  • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

• component a an amount of the order of 5 to 100% by weight of component a, of a nionionic surface active component having a cloud point below 35 C.
• component a an amount of the order of 1 to 50% by weight of component a, of a component selected from the group consisting of aliphatic monocarboxylic acids and aliphatic alcohols wherein the aliphatic radical contains 8 to 18 carbon atoms, and
• composition when said composition contains aliphatic monocarboxylic acid as component c, an amount of the order of 1 to 20 times the weight of component a of a mineral acid, preferably phosphoric acid.
• composition should also contain an iodine source providing an amount of available iodine of the order of 5 to 50% of the combined weight of components a and b.
• the new low foam detergent compositions of the present invention meet the long felt need above mentioned by providing a temperature coeflicient approaching unity throughout the 25 to 60 C. temperature range which characterizes most cleaning systems in which the cleaning solution is initially heated, but not thereafter reheated.
• compositions have now been discovered which at the intended use dilutions for cleaning and/or sanitizing purposes, produce very low foaming and show little significant change in the amount of foam or nature of the foam, i.e. its speed of breaking, throughout the 25 to 60 C. temperature range.
• the new low foam detergent compositions of the present invention comprise a uniquely balanced combination of high cloud point nonionic surface active component, low cloud point nonionic surface active component, defoamer selected from the class consisting of fatty acids and fatty alcohols, and a mineral acid in instances in which the defoamer is a fatty acid.
• active components can constitute the complete composition or water and/or solvent can be present; and when combined detergent-sanitizer action is desired, a source of available iodine can be included.
• the detergent composition is preferably prepared in concentrated form, intended for high dilution in making use solutions; and it is in the solutions that the low forming properties with little change in the amount or nature of foam throughout the 25 to 60 C. temperature range is of practical importance.
• the relative amounts or proportions of active components can best characterize the new composition in both concentrated or commercial product form and in the use dilutions thereof.
• the high cloud point surface active agent is usually the predominate detergent component the amounts of other active compo nents will be related to the parts by weight of said high cloud point material.
• the high cloud point nonionic surface active component can be one or more nonionic surface active agents having a cloud point of at least 45 C., and preferably at least 55 C., in 1% aqueous solution.
• Suitable nonionics of this type are those containing both ethylene oxide (E0) and propylene oxide (PO) groups, having a molecular weight of at least 1800, and suitably in 1800 to 6000 range, with the molecular weight of PO being at least 800, and the E0 being not more than 65% by weight of said component.
• the maximum amount of E0 In switching from lower to higher molecular weight materials, the maximum amount of E0 must be reduced. Thus, as the molecular weight of the PO portion increases from about 800 to 4000 the maximum amount of E0 should decrease from about 65 to 30%. Alkyl phenolethylene oxide condensates and fatty alcohol ethylene oxide condensates are not suitable high cloud point materials.
• Nonionic detergents which satisfy the conditions above noted are Pluronic L35, a condensate of ethylene and propylene oxides, having an average molecular weight of 1900, containing a propylene oxide prepolymer of about 950 molecular weight, and an amount of ethylene oxide equal to about 50% of the total weight of the detergent; Pluronic L44 which is a similar condensate having an average molecular weight of 2200, in which the propylene oxide nucleus has a molecular weight of about 1300 and the ethylene oxide content is about 40%; and Pluronic P123, a similar condensate having an average molecular weight of 5650, in which the propylene oxide nucleus has a molecular weight of about 4000, and the ethylene oxide content is about 30%. Even these detergent
• the low cloud point surface active component can be one or more nonionic surface active agents having a cloud point below about 35 C., and preferably below 25 C., in 1% aqueous solution. It should contain ethylene oxide in the amount of 2-25 moles per molecule of surfactant, and the surfactant in turn should have a molecular weight of at least 300, or at least 1800 when the detergent contains both ethylene oxide and propylene oxide. The amount of low cloud point surfactant should be of the order of 5% to 100% of the weight of high cloud point surfactant in the composition.
• Surface active agents with low cloud points are generally not phase stable, i.e. the separate or do not form homogeneous solutions, at product levels by themselves at temperatures above the cloud point, especially in compositions containing iodine, acids, water, etc. They do not dilute satisfactorily into aqueous solution at temperatures near or above their cloud point and, therefore, are totally unsatisfactory as single detergent constituents of cleaning compositions.
• these adverse properties are overcome and the combination provides detergency and satisfactory dilution at temperatures within the 25 to 60 C. range.
• Suitable low cloud point surface active agents falling within the limitation above described include ethoxylated nonylphenol and alcohols containing 2 to 4 moles of ethylene oxide, the E0 providing not more than 50% of the total weight, and a number of Pluronic type detergents which are condensates of ethylene oxide on a polypropylene oxide nucleus, and which contain less than 30% E0. Specific Pluronic type detergents which have been found satisfactory are:
• Pluronic IJI22 is preferred in that it requires a minimum amount of solvent to form homogeneous solutions. Furthermore, in compositions containing iodine it provides the most iodine color at high use dilution.
• the defoamer component can be one or more aliphatic monocarboxylic acids and/or aliphatic alcohols wherein the aliphatic radical contains 8 to 18 carbon atoms.
• the defoamers become increasingly resistant to solubilization both in 4 the product and in use dilutions, requiring the use of high concentrations of solvent; and at the lower end of the range the materials show reduced defoamer action (weight for weight). For these reasons aliphatic chains of 10 to 14 carbon atoms are preferred.
• the amount of defoamer should be of the order of 1% to 50% of the weight of high cloud point surfactant in the composition.
• the composition should also contain an amount of mineral acid of the order of 1 to 20 times the weight of said high cloud point surfactant.
• mineral acids such as hydrochloric, sulfuric, and phosphoric acids can be employed, but phosphoric acid is preferred in view of its relatively low molecular weight, and very low toxicity. While the mineral acid is needed in compositions containing aliphatic carboxylic acid defoamer, it is not needed in compositions containing aliphatic alcohol defoamer.
• acid or extra acid can always be employed, if desired, to provide an acid cleaning action, or to enhance the stability of iodine in detergent-sanitizer compositions.
• the composition may contain a water soluble solvent containing at least one alcoholic OH group.
• the amount of solvent is suitably about 1 to 10 times the weight of the high cloud point surfactant, but not more than about 50% of the total composition. When both solvent and acid are present the combined amounts thereof should not exceed about of the total weight of the composition.
• compositions according to the present invention are those having a combined low-foam detergent and sanitizer action.
• the nonionic surfactants above mentioned are complexing agents for iodine, and excellent sanitizing action is provided by incorporating in the composition a source iodine providing an amount of available iodine of the order of 5 to 50% of the combined weight of the high cloud point and low cloud point surfactants.
• the iodine can be introduced by dis solving elemental iodine in the surfactants, or preferably by adding to the surfactants an aqueous iodideiodine solution as described in US. Pat. No. 3,028,099.
• phosphoric acid When iodine is present, phosphoric acid, or mixtures of phosphoric and hydroxyacetic acids, provide enhancement of the iodine activity. It should be noted, however, that if the defoamer is an aliphatic monocarboxylic acid as above described, a minimum amount of phosphoric acid should be present in such acid mlxtures.
• either aliphatic acids or alcohols may be used as defoaming constituents.
• Aliphatic acids are preferred in those applications were food equipment is being cleaned.
• Aliphatic alcohols are preferred when highly alkaline waters are used to make dilutions. When the equipment to be cleaned is made of materials that corrode easily, such as aluminum, zinc or galvanized iron, then non-acid formulas with aliphatic alcohol are preferred.
• the composition When the composition is intended for use in equipment which is not sensitive to acid, supplemental amounts of acid may be included to obtain the desired product performance.
• supplemental amounts of acid may be included to obtain the desired product performance.
• the defoamer is an aliphatic alcohol, or an aliphatic carboxylic acid with mineral acid
• additional amounts of mineral acid or a carboxylic acid such as an hydroxyacetic, citric, lactic or malic acids may be used.
• compositions can be prepared for marketing in various concentrations with appropriate dilution schedules for preparing use solutions.
• dilution schedules for preparing use solutions.
• High cloud point surfactant 3-12 Low cloud point surfactant 0.5-5 Aliphatic acid or alcohol defoamer 0.025-2.5 Available iodine -5 Acid 0-50 Solvent 0-50 Water to 100%.
• 150 ml. of the solution to be tested is placed in a 500 ml. calibrated gas washing bottle with fritted cylinder. Using an air flow meter, the air flow is adjusted to 2 liters per minute and the foam height is read after equilibrium has been established at a temperature of 25 C.
• compositions that overflow the gas washing bottle (approximately 440 ml. of foam when considering the volume above the calibrations) in less than 15 seconds are unsatisfactory.
• the time of overflow can be recorded, as well as the collapse time of the foam within the cylinder.
• compositions which form a foam in 15 seconds and which take more than 1 minute to collapse are unsatisfactory.
• compositions which provide foam volumes in 15 seconds of not more than 350 ml., and a foam collapse time of not more than 25 seconds are generally satisfactory.
• the foam volume should be below about 200 ml. and the collapse time less than 15 seconds. With such performance, foaming is no longer a problem in dairy pipelines and other C-I-P equipment.
• the ability of the new compositions to approach a temperature coefiicient of unity is diificult to explain even after finding that it is possible.
• the high cloud point surfactants by themselves foam excessively for use in C-I-P equipment; and the addition of defoamer causes foam reduction principally at relatively low temperatures, with an increase in foam at elevated temperature.
• the low cloud point surfactant appears to act as a foam inhibitor for the high cloud point surfactant at elevated tempera- Amount by wt., percent 5 ture, while the latter acts to solubilize the former above its cloud point.
• the essential components i.e. the high and low cloud point surfactants, the aliphatic acid or alcohol, and the mineral acid (when needed) as herein described, provide a most unique and synergistic cooperation in the new compositions.
• compositions are prepared similar to composition 7 in Example I in which the 40% phosphoric acid component is varied as indicated in the following tabulation, and the several compositions are subjected to foam testing with the results shown. (Acid percentages are on anhydrous basis.)
• a detergent composition was prepared as described in Example I containing:
• the foam volume was 175 mls. which col- 255212 311 avmlable lapsed in 8 seconds.
• EXAMPLE VII Compositions containing fatty acid defoamer, but containing no iodine, were prepared according to the following formulation, and foam tested at 1:640 dilution as EXAMPLE VIII Compositions were prepared with different low cloud point surfactants, as indicated, and subjected to foam testing at 1:640 dilution as described in Example I giving l 0 EXAMPLE X A composition was prepared having the composition indicated below employing as the high cloud point surfactant a Pluronic type surfactant consisting of a polyoxypropylene base having a molecular weight of about 1200 condensed with ethylene oxide to provide approximately 35% of the weight of the surfactant.
• Pluronic type surfactant consisting of a polyoxypropylene base having a molecular weight of about 1200 condensed with ethylene oxide to provide approximately 35% of the weight of the surfactant.
• compositions similar to those in Example VIII, but containing a different high cloud point surfactant, were prepared and foam tested at 1:640 dilution as described in Example I with the following results:
• Percent Pluronic L35 and Pluronic L44 having cloud points of 76 C. and 6 5 C. respectively are preferred high cloud point surfactants.
• the examples thus far have employed aliphatic carboxylic acids as the defoaming component.
• the following examples relate to similar compositions containing aliphatic alcohols, or mixtures of aliphatic acid and alcohol as the defoaming component.
• the mineral acid is not necessary; in fact it is possible to prepare alkaline cleaners as shown in Example XIV.
• acid can be added, and the presence of acid generally improves performance.
• Such acid can be a mineral acid such as phosphoric, sulfuric or hydrochloric acid, or carboxylic acids such as hydroxyacetic, citric, lactic, or malic acid, or mixtures thereof.
• EXAMPLE XII Compositions were prepared having the formulations indicated below and subjected to foam testing at 1:640 dilution in the manner previously described giving results as shown in the following tabulations.
• EXAMPLE XIII A series of compositions was prepared each containing by weight 7% Pluronic L35, 2% Pluronic L122, 40% H PO and 1.75 available iodine, together with aliphatic alcohol of the type and amount indicated below, plus 4% isopropyl alcohol and butyl Cellosolve, the balance to 100% being water. These compositions, at 1:640 dilution, were subjected to foam testing as in Example I giving the results tabulated below.
• EXAMPLE XV A composition of the following formulation, containing both fatty acid and fatty alcohol as defoamer, was prepared and tested for foaming at 1:640 dilution with the results indicated below:
• a nonionic surface active component having a cloud point above 45 C. in a 1% aqueous solution, a molecular weight in the range of 1800 to 6000, and containing both propylene oxide (PO) and ethylene oxide (E0) groups with the molecular weight of PO being at least 800, and the E0 being not more than 65% by weight of said component,
• component a an amount of the order of 5 to by weight of component a, of a nonionic surface active component having a cloud point below 35 C. in a 1% aqueous solution and containing 2 to 25 moles of EO per molecule of said nonionie component, and said nonionie component having a minimum molecular weight of 300,
• component a an amount of the order of l to 50% by weight of component a, of a component selected from the group consisting of unsubstituted aliphatic monocarboxylic acids and unsubstituted aliphatic alcohols wherein the aliphatic radical contains 8 to 18 carbon atoms, and
• composition when said composition contains aliphatic monocarboxylic acid as component c, an amount of the order of 1 to 20 times the weight of component a of a mineral acid selected from the group consisting of hydrochloric acid, sulfuric acid and phosphoric acid, said detergent composition being characterized in that the nature and degree of foaming it exhibits at temperatures of from about 25 to 60 C. is substantially uniform such that it provides a substantially unitary temperature coefficient.
• Low foam detergent composition as defined in claim 1 wherein component c is decyl alcohol.
• Low foam detergent composition as defined in claim 1 wherein component 0 is tridecyl alcohol.
• Low foam detergent composition as defined in claim 1 wherein component c is an aliphatic alcohol, and said composition contains an additive selected from the group consisting of caustic, alkaline salts, and mixtures thereof to provide an alkaline formulation.
• component b has a minimum molecular weight of 1800 when both EO and PO groups are present.
• component b is a nonylphenol-ethylene oxide condensate.
• component b has a base of polyoxypropylene having ethylene oxide condensed therewith.
• low foam detergent composition as defined in claim 1 wherein the nonionic surface active agent of component a is a condensate of polyoxypropylene having a molecular weight of about 950 with an amount of ethylene oxide to provide about 50% of the weight of said nonionic surface active agent, and component b is a condensate of polyoxypropylene having a molecular Weight of about 4000 with an amount of ethylene oxide to provide 20% of the weight of said nonionic.
• low foam detergent composition as defined in claim 1 wherein the nonionic surface active agent of component a is a condensate of polyoxypropylene having a molecular weight of about 1200 with an amount of ethylene oxide to provide about 40% of the weight of said nonionic surface active agent, and component b is a condensate of polyoxypropylene having a molecular weight of about 4000 with an amount of ethylene oxide to provide 20% of the Weight of said nonionic.
• Low foam detergent composition as defined in claim 1 wherein said composition includes a source of iodine in an amount sufficient to provide a quantity of available iodine of from about 5 to 50% of the combined Weight of components a and b.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (15)

Cited By (31)

Families Citing this family (6)

• 0
  • DK DK133826D patent/DK133826A/da unknown
• 1968
  • 1968-07-25 US US747427A patent/US3650965A/en not_active Expired - Lifetime
• 1969
  • 1969-07-15 IL IL32626A patent/IL32626A/xx unknown
  • 1969-07-16 NO NO02971/69A patent/NO126275B/no unknown
  • 1969-07-22 SE SE6910314A patent/SE364522C/xx unknown
  • 1969-07-22 CH CH1119269A patent/CH539116A/de not_active IP Right Cessation
  • 1969-07-24 IE IE1033/69A patent/IE33243B1/xx unknown
  • 1969-07-24 ES ES369852A patent/ES369852A1/es not_active Expired
  • 1969-07-24 DK DK400169AA patent/DK133826B/da unknown
  • 1969-07-24 DE DE19691937682 patent/DE1937682A1/de active Granted
  • 1969-07-24 BE BE736509D patent/BE736509A/xx unknown
  • 1969-07-24 NL NL6911409.A patent/NL163823C/xx not_active IP Right Cessation
  • 1969-07-24 FR FR6925341A patent/FR2013695A1/fr not_active Withdrawn
  • 1969-07-24 AT AT714669A patent/AT297192B/de not_active IP Right Cessation
  • 1969-07-25 BR BR211029/69A patent/BR6911029D0/pt unknown
  • 1969-07-25 GB GB37466/69A patent/GB1280034A/en not_active Expired

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