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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • 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
  • C11D1/37—Mixtures of compounds all of which are anionic
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • 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
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
• • 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
  • C11D1/75—Amino oxides

Definitions

• Liquid detergent compositions having excellent sudsing and mildness characteristics and consisting essentially of (1) from about 8% to about 35% of an alkyl ether sulfate obtained by sulfating and neutralizing the condensation product of from about to about 12 moles of ethylene oxide and 1 mole of a high molecular weight alcohol having from about to about 16 carbon atoms; (2) an alkyl sulfate having the formula ROSO -M wherein R is alkyl having from about 10 to about 16 carbon atoms; and M is a salt-forming cation; the ratio of said alkyl ether sulfate to said alkyl sulfate being from about 2:1 to about 6:1 and the balance being water.
• the compositions have a desirable balance of cleaning, sudsing and mildness properties and are particularly useful in dishwashing and light-duty laundering situations.
• This invention relates to liquid detergent compositions. More particularly it relates to liquid detergent compositions comprising a mixture of surface-active compounds having exceptional sudsing and mildness characteristics.
• the quantity and persistence of suds are very important in light-duty liquid detergent compositions intended for dishwashing and the like. Frequently, the detergent capacity of a washing solution is gauged by the user by the amount of suds present and the persistence of suds for a reasonable period of time. Since the washing of dishes frequently constitutes exposure of the hands to a detergent solution, a suitable detergent composition must additionally be characterized by mildness to the skin. The attainment of the combined properties of desirable sudsing and mildness levels in liquid detergent compositions is a matter of difiicult formulation. Liquid compositions 113N- ing high sudsing qualities are often harsh on the skin.
• liquid compositions characterized by desirable mildness to the hands of the user are frequently deficient in their sudsing and/ or detergent qualities.
• the present invention is based in part on the discovery that the sudsing qualities of a liquid detergent composition containing a sulfated and neutralized ethoxylate of from about 5 to about 12 moles of ethylene oxide per mole of high molecular weight alcohol can be substantially improved by addition of an alkyl sulfate detergent with retention of desirable mildness properties.
• the present invention enables the provision of lightduty liquid detergent compositions having excellent sudsing and mildness properties.
• These compositions consist essentially of:
• alkyl ether sulfate obtained by sulfating and neutralizing the condensation product of from about 5 to about 12 moles of ethylene oxide and 1 mole of a high molecular weight alcohol having from about 10 to about 16 carbon atoms and having the formula where R is alkyl having from about 10 to about 16 carbon atoms; M is a salt-forming cation; and r has an average value of from about 5 to about 12;
• compositions of the invention as defined hereinbefore are characterized by excellent detergent, sudsing and mildness properties.
• the sulfated and neutralized ethoxylate detergents of the invention are well known. Their preparation and properties are described, for example, in British Pat. 791,704 (Mar. 12, 1958); British Pat. 797,119 (June 25, 1958); US. Pat. 3,179,599 to Eaton et al. (Apr. 20, 1965 The Journal of the American Oil Chemists Society, 36, pp. 241-244 (June 1959); The Journal of the American Oil Chemists Society, 37, pp. 472-430 (September 1960); and The Journal of the American Oil Chemists Society, 45, pp. 738-741 (November 1968).
• alkyl ether sulfates These detergents, termed hereinafter for convenience as alkyl ether sulfates, are employed in the compositions of the invention in an amount of from about 8% to about 35% by weight.
• the alkyl ether sulfates of the invention correspond to the formula hereinbefore described.
• the designation of the value of r as an average value of from about 5 to about 12 refers to the number of moles of ethylene oxide reacted per mole of high molecular weight alcohol to form the ethoxylated alcohol product which is subsequently sulfated and neutralized to provide the alkyl ether sulfate component of the invention.
• the alkyl ether sulfate component comprises a mixture of water-soluble salts.
• This mixture comprises a distribution of alkyl ether sulfate detergent molecules of varying ethylene oxide content.
• the resulting ethoxylated alcohol reaction product is comprised of a mixture of ether molecules having varying numbers of ethylene oxide groups.
• the mixture will contain a mixture of ether compounds wherein the mono-(ethylene glycol)- ether derivative is present admixed with alkyl ether compounds containing a variable number of ethylene oxide groups extending from alkyl di-(ethylene glycol) ether to an alkyl poly-(ethylene glycol) ether wherein the number of ethylene oxide groups is equal to or greater than about twice the number of moles of ethylene oxide reacted with the high molecular alcohol.
• the product having a number of ethylene oxide groups equal to the number of moles of ethylene oxide reacted with high molecular weight alcohol tends to predominate.
• the designation hereinafter of r as being 5 or 12 refers, respectively, to the alkyl ether sulfate detergent product which is the result of sulfation and neutralization in a known manner of an ethoxylated condensate derived from reaction of 5 or 12 moles, respectively, of ethylene oxide per mole of high molecular weight alcohol.
• the alkyl ether sulfate component of the invention comprises from about 8% to about 35% by weight of the liquid detergent composition of the invention. Preferred from the standpoints of desirable sudsing and economic considerations is an amount of from about 15% to about 25%.
• the alkyl ether sulfates of the invention can be prepared by sulfation and neutralization of a condensate prepared by reaction of from about 5 to about 12 moles of ethylene oxide per mole of a monohydric alcohol having from about 10 to about 16 carbon atoms.
• Suitable alcohols for preparation of the condensate include those derived from fats and synthetic alcohols. Examples of these alcohols include decyl alcohol, dodecyl alcohol, oxobased tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol and alcohols derived by reducing fatty oils such as coconut oil, palm oil, kernel oil, babassu oil, coconut fatty acids or their alkyl esters.
• alkyl is intended to include the olefinic as well as true alkyl groups and includes those derived from fatty origin such as oleyl alcohol and the like.
• Sulfation and neutralization of the condensation products of ethylene oxide and higher molecular alcohol, described hereinbefore, can be conducted by known methods.
• the condensation of ethylene oxide and alcohol, such as middle-cut fatty alcohol from coconut oil, can be carried out in an autoclave in the presence of an alkaline catalyst such as sodium hydroxide.
• the condensation can also be carried out using acidic catalysts such as stannic chloride or boron trifluoride, which provide condensates at lower temperatures and pressures.
• Sulfation of the condensate of fatty alcohol and ethylene oxide can be carried out batchwise or continuously employing chlorosulfonic acid or sulfur trioxide. A temperature of from about 75 F. to 135 F. is suitable for this purpose.
• the sulfated product is neutralized by reaction with an alkali metal base, (e.g. sodium hydroxide, potassium hydroxide) ammonium hydroxide or alkylolsubstituted ammonias.
• an alkali metal base e.g. sodium hydroxide, potassium hydroxide
• ammonium hydroxide or alkylolsubstituted ammonias e.g. sodium hydroxide, potassium hydroxide
• Preferred alkylol-substituted ammonias are mono-, di-, and tri-ethanol amines, mono-, di-, and tri-isopropanol amines and mono-, di-, and triglycerol amines, i.e., those in which the alkylol group has from 2 to 3 carbon atoms.
• M in the hereinbefore described formula will be a water-solubilizing cation such as sodium, potassium, ammonium, trimethanolamine or the like.
• alkyl ether sulfates in liquid detergent compositions, compositions having both improved mildness and sudsing properties have been difficult to formulate.
• the improvement in detergent and/ or sudsing properties obtained by employing an alkyl ether sulfate derived from an ethoxylate of 3 moles per mole of high molecular alcohol has been at the expense of reduced mildness.
• an alkyl ether sulfate derived from a condensate of 6 moles ethylene oxide per mole of alcohol and an alkyl sulfate enables the formulation of detergent compositions having sudsing qualities equal to those based upon an alkyl ether sulfate product derived from a condensate of 3 moles ethylene oxide per mole of alcohol while retaining the mildness levels of the alkyl ether sulfate component. Accordingly, the combined use of an alkyl ether sulfate component as hereinbefore described and an alkyl sulfate detergent enables the formulation of light duty liquid detergent compositions having a desirable balance of both sudsing and mildness properties.
• the alkyl sulfate component of the present invention conforms to the following formula ROSO M wherein R and M are as defined hereinbefore.
• the alkyl sulfate component of the invention is employed in an amount which provides a ratio of alkyl ether sulfate to alkyl sulfate of from about 2:1 to about 6: 1.
• a preferred ratio is from about 2.5 :1 to about 5:1 and provides an optimum balance of sudsing and mildness properties.
• the compositions of the invention will contain from about 1.5% to about 12% of alkyl sulfate.
• the alkyl ether sulfate component of the invention will comprise a'mixture of sulfate detergent molecules. To the extent that such mixture will contain a minor amount of alkyl sulfate wherein no ethylene oxide groups are present, the presence of minor amounts of such compounds can be taken into consideration in preparing the compositions of the invention.
• the hereinbefore specified amounts of alkyl sulfate refer to the presence of alkyl sulfate exclusive of any alkyl sulfate which may comprise a portion of the alkyl ether sulfate component.
• alkyl ether sulfate components of the invention do not alone provide a desirable level of sudsing properties, the incorporation of alkyl sulfate is essential to the attainment of the desired balance of sudsing and mildness qualities characteristic of the compositions of the invention.
• the detergent compositions of the invention can be formulated by conventional methods.
• the alkyl ether sulfate, alkyl sulfate and optional components can be incorporated into aqueous solution individually or in combination.
• the alkyl sulfate and alkyl ether sulfate components are preferably added in admixture.
• a preferred means of effecting simultaneous addition involves preparation in situ of alkyl sulfate during the preparation of the alkyl ether sulfate component. This can be effected by addition of an alcohol of from about to about 16 carbon atoms to an ethoxylated product obtained by the condensation of from about 5 to about 12 moles of ethylene oxide per mole of alcohol.
• the detergent compositions of the invention can contain any of the usual detergent adjuvants.
• solubilizing agents for example, solubilizing agents, viscosity control agents such as toluene sulfonates and xylene sulfonates, perfumes, anti-tarnishing agents, opacifiers such as ethylene glycol distearate or polystyrene, inert salts such as sodium sulfate, anti-redeposition agents, bacteriostatis agents, dyes, fluorescers, suds builders, and the like, can be utilized herein without detracting from the advantageous properties of these compositions.
• Suitable solubilizing agents include methyl, ethyl, n-propyl and isopropyl alcohols and are employed in an amount of from about 5% to 12% of the composition of the invention.
• compositions of the invention in addition to the presence of the alkyl ether sulfate and alkyl sulfate components described hereinbefore, can contain water-soluble detergent compounds.
• Suitable detergents are those which do not interfere with the desirable detergent, sudsing and mildness properties of the compositions of the invention.
• Such materials should be employed in non-interfering amounts so as to avoid the minimization or masking of the advantageous properties of the combined alkyl ether sulfate and alkyl sulfate components of the invention.
• Suitable water-soluble. detergents include anionic (e.g.,-
• nonionic e.g., alkylene oxide condensates of aliphatic and alkyl aromatic compounds
• ampholytic e.g., sodium 3-dodecylaminopropionate
• zwitterionic e.g
• olefin sulfonates are the olefin sulfonates having from aboutlo to about 24 carbon atoms and obtained by sulfonation of OL-OICfiIlS with gaseous sulfur trioxide. These include the alkali metal and ammonium tetradecene and hexadecene sulfonates. Other examples are described in US. 3,332,880 (July 25, 1967).
• Preferred detergents herein include the alkyl glyceryl ether sulfonates, trialkyl amine oxides, olefin sulfonates andzwitterionic detergents. Mixtures of these detergents can be employed.
• a preferred embodiment of the present invention comprises a liquid detergent composition consisting essentially of from about to about of an alkyl ether sulfate having the formula wherein R is a straight-chain alkyl having from about 12 to about 14 carbon atoms, M is alkali metal or ammonium and r has an average value of from about 5 to about 12; an alkyl sulfate having the formula ROSO M wherein R and M are as defined above and the ratio of said alkyl ether sulfate to said alkyl sulfate is from about D-Amrnonium alkyl sulfate 2.521 to about 5:1; from about 2% to about 6% of an alkyl glyceryl ether sulfonate having
• compositions provide excellent cleaning, sudsing and mildness qualities and are particularly suited for dishwashiug and light-duty fabric laundering.
• compositions containing varying amounts of the following components were prepared: (A) the ammonium salt of the sulfated condensation product of one mole of middle-cut coconut alcohol containing 2% C 66% C 23% C and 9% C alkyl groups with 3 moles of ethylene oxide; (B) the ammonium salt of the sulfated condensation product of one mole of the same middle-cut coconut alcohol and 6 moles of ethylene oxide; (C) the ammonium salt of the sulfated condensation product of one mole of the same middle-cut coconut alcohol and 12 moles of ethylene oxide; and (D) ammonium alkyl sulfate wherein the alkyl is derived from the same middle-cut coconut alcohol.
• compositions also contained the following components in the stated proportions: (E) sodium alkyl glyceryl ether sulfonate wherein the alkyl is derived from the same middle-cut coconut alcohol; and (F) a tertiary amine oxide having a long alkyl chain derived from the same middle-cut coconut alcohol and two methyl groups.
• B-Ammonium alkyl (CzH4O)s sulfate O-Ammouium alkyl (021340) sulfate ESodium alkyl glyceryl ether sulfonate. Facocimubalkyl dimethyl amine oxide ano Ethylene glycol distearate Miscellaneous (brightener, perfume, e Water, balance to parts
• 7 cc. of each of the compositions was added to a dishpan containing one gallon of water with a hardness of 7 grains at a temperature of F, and a pH of 8. Suds were generated by mechanical agitation (small propeller) and the suds level measured.
• compositions of the invention are characterized by sudsing properties (speed and stability) which are superior to comparable compositions containing an ammonium salt of a sulfated condensate of one mole middle-cut coconut alcohol and 6 moles ethylene oxide (Composition 4) or an ammonium salt of a sulfated condensate of one mole middle-cut coconut alcohol and 12 moles ethylene oxide (Composition 5). Particularly significant is the shorter period of time required to generate two inches of suds.
• compositions of the invention compare in sudsing performance to compositions containing a conventional alkyl ether sulfate, i.e., an ammonium salt of the sulfated condensate of one mole middle-cut coconut alcohol and 3 moles ethylene oxide (Composition 3).
• a conventional alkyl ether sulfate i.e., an ammonium salt of the sulfated condensate of one mole middle-cut coconut alcohol and 3 moles ethylene oxide (Composition 3).
• the sudsing characteristics of the compositions of the invention are particularly significant in view of the amounts of detergent active in Compositions 1 and 2 which provide greater sudsing performance per part of detergent active than Composition 3.
• the excellent sudsing performance per part of detergent active represents a significant cost advantage.
• Elbow-crease wash test A panel of ten subjects is employed in each test. The inner aspect of a subjects elbow is washed for 30 seconds with a small terry cloth washcloth saturated with a warm solution of the detergent compositions to be tested. The resulting lather is allowed to remain in contact with the skin for an additional 30 seconds. The area is blotted dry with a paper towel. The washing procedure is carried out three times daily for each of four consecutive days and two times the following day. Before each washing, the inside of the elbow is graded for over-all skin condition using a standard 1 to 10 scale where 10 represents no sign of any irritation and 1 represents severe irritation. A grade of 7 represents moderate irritation. The subjects skin is graded after the final washing. The grades for each subject are averaged. A control composition is concurrently evaluated in the same manner by washing the subjects other arm. A composition is considered to be milder than a control composition if a difference of 0.5 or greater is present.
• Hand immersion test A panel of six subjects is employed in each test. The subjects hand is soaked in an immersion tank containing a 2% solution of the composition to be tested. The hand is soaked for 30 minutes each day for a five-day period. Solution temperature is held at 105 F. The solution is continuously stirred with a magnetic stirrer. The subjects hand is rinsed and wiped dry following the soaking period. The subjects hand is graded microscopically for scaliness and visually for erythema prior to the initial washing and approximately five hours after each washing. The condition of the skin is graded on a descending scale where 10 represents no scaliness or irritation. A grade of 6 represents a moderate irritation. A control composition is evaluated concurrently using. the subjects other arm. At the end of each test, the grades (both for scaliness and erythema) for each subject are averaged. A composition is considered to be milder than a comparative composition if a difference of 0.5 or greater is present.
• Arm immersion test The arm immersion test is conducted in the same manner as the hand immersion test described hereinbefore, except that the subjects arms are immersed from the elbow to the hand in troughs containing the compositions to be evaluated. The subjects arms are evaluated for scaling and erythema.
• composition 1 of the invention was evaluated for mildness characteristics and compared with a similar composition free of additional ammonium alkyl sulfate (Composition 4). The results are tabulated as follows:
• compositions 1 and 2 of the invention were evaluated for mildness and compared with compositions containing a conventional alkyl ether sulfate, i.e., the ammonium salt of the condensate of 1 mole middle-cut coconut alcohol and 3 moles ethylene oxide (Composition 3).
• a conventional alkyl ether sulfate i.e., the ammonium salt of the condensate of 1 mole middle-cut coconut alcohol and 3 moles ethylene oxide
• compositions of the invention are characterized by improved mildness properties.
• sulfate and, sulfonate detergent surfactants in the preceding example are the monoethanolamine, diethanolamine, triethanol amine, or potassium salts, substantially equivalent results are achieved.
• Compositions Components 6 7 A.A.mmonium alkyl (CH4O)a sulfate 13 O-Ammonium alkyl (CzH40)12 sulfate" 9.8 DAmmonium alkyl sulfate 3. 2 F-Coeonut-alkyl dimethyl amine oxide 2. 75 2. 75 3-(N,N-dimethylN-alkylam monio)-2-hydroxypropane-l-sultonate (wherein the alkyl is the same as in Components A, C, D and F) 4. 25 4. 25 Sodium salt, of olefin sulfonate (from 50:50 mixture of On and On a-olefins) 21. 21. 0 Ethanol 10. 10. 5 Miscellaneous (electrolyte, perfume, etc.) 1 Water, balance to 100 parts Compositions 6 and 7 were mildness tested employing the Elbow-Crease Wash Test. The results are tabulated as follows:
• composition 6 The composition of the invention (Composition 6) was milder than a composition containing ammonium alkyl (C H.,O) sulfate (Composition 7).
• compositions 6 and 7 were tested for sudsing properties according to the test method hereinbefore described.
• the following data represents an average of two such tests:
• R(OC H ),--OSO M wherein R is alkyl having from about 10 to about 16 carbon atoms; M is a salt-forming cation; and r wherein R is alkyl having from about '10 to about 16 carbon atoms; and M is a salt-forming cation;
• ratio of said alkyl ether sulfate to said alkyl sulfate being from about 2:1 to about 6: 1;
• composition of claim 1 wherein the alkyl ether sulfate has the formula wherein R is a straight-chain alkyl having from about 12 to about 14 carbon atoms and at least 50% of said alkyl groups have 12 carbon atoms; and M is ammonium.
• composition of claim 2 wherein the ratio of alkyl ether sulfate to alkyl sulfate is from about 2.5:1 to about 5:1.
• composition of claim 3 wherein the alkyl sulfate has the formula ROSO M wherein R is a straight-chain alkyl having from about 12 to about 14 carbon atoms and at least 50% of said alkyl groups have carbon atoms; and M is ammonium.
• alkyl glyceryl ether sulfonate is sodium alkyl glyceryl ether sulfonate and the alkyl group contains from about 12 to about 14 carbon atoms with at least 50% of said alkyl groups having 12 carbon atoms; and wherein the trialkyl amine oxide is alkyldimethyl amine oxide and the alkyl group contains from about 12 to about 14 carbon atoms with at least 5 0% of said alkyl groups having 12 carbon atoms.
• composition of claim 5 additionally containing from about 5% to 12% of a solubilizing agent selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and mixtures thereof.
• a solubilizing agent selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and mixtures thereof.
• composition of claim 4 additionally containing from about 5% to 12% of a solubilizing agent selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and mixtures thereof.
• a solubilizing agent selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and mixtures thereof.

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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)
• Detergent Compositions (AREA)

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Cited By (28)

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• 0
  • BE BE759280D patent/BE759280A/xx unknown
• 1969
  • 1969-11-24 US US00879522A patent/US3793233A/en not_active Expired - Lifetime
• 1970
  • 1970-11-17 SE SE7015532A patent/SE371206B/xx unknown
  • 1970-11-21 DE DE2057353A patent/DE2057353B2/de not_active Withdrawn
  • 1970-11-23 IE IE1494/70A patent/IE34751B1/xx unknown
  • 1970-11-23 NL NL7017088A patent/NL7017088A/xx not_active Application Discontinuation
  • 1970-11-23 AT AT1052770A patent/ATA1052770A/de not_active Application Discontinuation
  • 1970-11-23 DK DK594670AA patent/DK134239B/da unknown
  • 1970-11-23 FR FR7042029A patent/FR2072266A5/fr not_active Expired
  • 1970-11-24 ES ES385838A patent/ES385838A1/es not_active Expired
  • 1970-11-24 GB GB5582770A patent/GB1321637A/en not_active Expired
  • 1970-11-24 JP JP45103587A patent/JPS4825043B1/ja active Pending
  • 1970-11-24 CH CH1739370A patent/CH547347A/xx not_active IP Right Cessation

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