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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

• the present invention relates, in general, to compositions advantageously adapted for use in connection with fabric washing and bleaching operations and the like and in particular to the provision of specific compounds and compositions for such purposes, said compositions being characterized in having an exceptionally high order of bleaching activity.
• bleaching agents as an adjunct to fabric washing operations is, of course, a well established practice and, in many instances, a recognized necessity.
• many of the detergent formulations currently available commercially include pre-determined quantities of bleaching agent as an essential ingredient; specific representatives of bleaching agents found to be suitable in this regard are well known in the art being extensively described in the prior art both patent and otherwise and include, for example, the chlorine bleaches, e.g., the alkali metal hypochlorites; active oxygen releasing peroxide compounds, e.g., inorganic persalts such as perborate, percarbonates, perphosphates, persilicates, persulfates, hydrogen peroxide, sodium peroxide and the like.
• peroxide type bleaching agents are, in general, preferred for use being found to be markedly superior as regards capability of providing a fabric having a softer hand, im-
• washing operation requiring comparatively high order of bleaching activity at reduced temperature ranges invariably necessitate the use of bleaching agents other than those of the peroxide type despite the attendant disadvantages necessarily involved, i.e., with respect to possibleimpairment of fabric strength, inferior resistance to discoloration, etc.
• activator compounds of this type function function as a precursor system by which the in situ generation of species cabable of effective bleaching action is made possible.
• activator compounds comprising acylated molecules of various types which, according to theoretical exposition, are alleged to fonn peracid species as a result of interaction with the bleaching agent, the peracid serving as bleaching agent.
• the effectiveness of the activator would in turn depend upon the strength of the peracid generated in situ this of course being related to thepKa of such acid. Regardless of the theory involved, experience establishes that significant enhancement of the bleaching capacity of peroxide compounds is obtained with the conjunctive use of auxiliary compounds of this type.
• a primary object of the present invention resides in the provision of activator compounds specifically and advantageously adapted for conjoint use with peroxide compounds in bleaching and washing compositions wherein one or more of the foregoing disadvantages are eliminated or at least mitigated to a substantial degree.
• Another object of the present invention resides in the provision of activator compounds capable of augmenting the bleaching capacity of peroxide compounds to the extent that such materials are rendered feasible for use in connection with washing operations under tepid temperature conditions.
• a further object of the present invention resides in the provision of activator compounds capable of synergistically enhancing the bleaching activity of peroxide compounds, the increase in bleaching activity being obtained despite the use of such activator in relatively low concentrations.
• a still further object of the present invention resides in the provision of activator compounds as well as washing and bleaching compositions containing same capable of yielding fabric materials having satisfactory absorbency, softness of hand, resistance to discoloration during wash cycle and upon aging.
• activator compounds for use in conjunction with peroxide type bleaching agents, said activators comprising compounds of the following formula:
• X represents halogen,e.g., chloro, bromo, etc. and Z represents the atoms necessary to complete a heterocyclic nucleus selected from the group consisting of a hydantoin or succinimide.
• peroxide quantities sufiicient to yield a concentration of only 2-4 parts of available oxygen per million parts of wash solution.
• peroxide quantities sufficient to yield available oxygen concentrations ranging from about 2 to about ppm in wash solution are found to be eminently suitable for the vast majority of laundering operations.
• the relative concentration of activator compound and bleaching agent employed is of primary importance in the tergent composition components e.g. synthetic detergent, soap, builder salts, soil suspending agents, brighteners, bacteriocides, bacteriostals, anti-oxidants etd, and the like.
• the composition may consist entirely or substantially (e.g. 50-100 percent) of the peroxygen compound and activator or alternatively there may be added inert filler or other non-interfering ingredients so that the peroxygen-activator combination comprises a minor fraction of the total composition (e.g. l-SO percent by weight thereof).
• the peroxygen-activator combination may comprise from about 1-75 percent by weight of the total composition with 2-50 percent preferred and 5-40 percent being most preferred.
• the balance of such fonnulations comprises the usual ingredients i.e. detergent, builder, etc. in the conventional concentrations e.g. detergent 5-75 percent by weight, builder 5-75 percent by weight, fillers 0-75 percent by weight and minor amounts e.g. 0.1 to 10 percent by weight of other adjuvants such as soil suspending agents, brighteners, anti-oxidants, etc.
• the test fabric comprises 3 X 6 inch coffee/tea-stained swatches as (cotton).
• the tergotometer receptacle containing the test swatches and activated perborate detergent solution is agitated (75rpm) for a period of 10 minutes. After a rinse, the load is dried and evaluated. Reflectance readings are taken both before and after completion of the immersion treatment, the numerical difference between readings being recorded as A Rd.
• the results obtained are itemized in the following table:
• the activator should be utilized in amounts sufficient to yield a mole ratio of perborate to activator with the range of from about 0.5:] to about 6:1.
• specific values may be selected in accordance with the bleaching problem to be negotiated; however, it is usually found that optimization of bleaching activity can be obtained by utilizing a perborate/activator mole ratio which approximate 1:1.
• specific and unusual situations may arise dictating departures from use of the optimum ratio in order to suppress, for example, deleterious effects with regard to certain types of dyed fabrics.
• the bleaching compositions of this invention may be employed in various forms such as powders, tablets and the like with or without additional non-interfering ingredients such as inert fillers e.g. sodium sulfate, sodium chloride, etc, conventional de- As the above data make manifestly clear, efficient bleaching activity is obtained despite an available oxygen concentration of only 4 ppm. Moreover, the reflectance values itemized as ARd are markedly superior to corresponding values obtained with analogous activator compounds typical of those described in the prior art when subjected to the identical testing procedure utilizing the identical compo-sitions itemized in the table.
• the ARd value measurement of 4 obtained in example 1 comprises a significantly high value in view of the minimal concentration of available oxygen as well as relatively mild temperature F., at which the testing is carried out. Such value would indicate substantial bleaching activity and especially in view of the somewhat limited period of washing 10 minutes).
• the 1:] mole ratio value would be recommended for most home laundering operations; as a matter of pure economics, excess perborate should be avoided since correlative enhancement of bleaching activity for given increases in concentrations is not attainable thereby.
• the improvement in reflectance values are similar to those summerized in Table 1.
• the above data establish marked superiority for the activators of the subject invention; the contrast being particularly striking at available oxygen concentrations approximating 7 ppm.
• the margin of improvement with respect to ARd diminishes with a perborate/activator mole ratio approximating 2:1; similarly, the ARd value increases with increasing concentrations of activator and perborate and particularly when the 1:1 mole ratio value is maintained.
• the activator material employed in each of the treatments comprises chlorobenzoylsuccinimide; perborate/activator mole ratios are varied as specified in the table. In order to permit a more comprehensive determination of the effects attending varying mole ratios, the procedure is carried out utilizing detergent to TABLE 4 Ex. Mole ratio Moles of Color no. perborate] perborate difference activator units rd.
• the low temperature efficiency of the bleach/activator systems described herein at low concentrations of available oxygen is thus self-evident.
• the N-m-halobenzoylimide activator compounds may be beneficially applied to bleaching operations at higher temperatures, i.e., within the range of from about 120 140 F. and higher, by simply increasing the available oxygen concentration. Again, optimum results are assured by the utilization of a mole ratio of perborate to activator in the range of 1:1. Therefore, by merely varying the quantity of perborate, it becomes possible to provide a composition specifically and advantageously adapted to either hot or cold water processing depending upon the requirements of the user.
• the A Rd value of approximately 2 with the use of an available oxygen concentration of only 2ppm, although somewhat reduced in comparison to the other values itemized is nevertheless highly significant when considered in view of the reduced temperature of 80 F. employed.
• the laundered fabric obtained be devoid of any significant yellowing tendency; thus, optimum whitening effects usually characterize those fabric materials bluish-white in appearance.
• the appearance of the laundered fabric is of critical importance from this standpoint.
• many of the activator compounds currently available commercially impart to the fabric material an undesired shift in whiteness to yellow. In many instances, this is a direct consequence of the necessity of employing the activator compound as well as perborate bleaching agent in inordinately high concentrations. Similar results are obtained in those instances wherein the activator and/or perborate concentrations are insufiicient to afford the requisite level of bleaching activity.
• the superior capability of the activators described herein to provide significant bleaching is illustrated in the following examples.
• the testing procedure described in example 1 is followed, i.e., with regard to the detergent compound employed, period of immersion agitation treatment, soiled fabric, etc.
• the available oxygen derived from the sodium perborate is maintained at a constant level of 16 ppm.
• the amount of activator is varied in order to yield the desired mole ratio. Increasing values of Ab, negatively, correspond to greater bluing and thus absence of yellowing, the numerical indicia assigned providing a relative assessment of such property.
• the activator compound employed comprises N-m-chlorobenzoylsuccinimide. The results obtained are summarized in the following table:
• watersoluble peroxide bleaching agents contemplated for use in accordance with the present invention can be defined as those compounds which give use to hydrogen peroxide when dissolved in water. Thus, such compounds are believed to contain hydrogen peroxide of crystallization.
• compositions described herein can be provided in the form of a bleaching composition or alternatively in the form of a built detergent product.
• Organic detergents which may be utilized for purposes encompass a relatively wide range of materials and may be of the anionic, non-ionic, cationic or amphoteric types.
• the anionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, phosphonate and phosphate. Examples of suitable anionic detergents which fall within the scope of the invention include the soaps.
• water-soluble salts of higher fatty acids or rosin acids such as may be derived from fats, oils, and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about 8 to 26, and preferably about 12 to 22, carbon atoms to the molecule.
• suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms, in the alkyl group in a straight or branched chain, e.g., the sodium salts of decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, or hexadecyl benzene sulfonate and the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl napthalene sulfonate, and sodium dinonyl napthalene sulfonate.
• the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sul
• olefin sulfonates including long chain alkene sulfonates, long chain hydroxy-alkanesulfonates.
• paraffin sulfonates such as the reaction products of alpha olefins and bisulfites (e.g. sodium bisulfite), e.g. primary paraffin sulfonates of about 10 20, preferably about 15-20, carbon atoms; sulfates of higher alcohols; salts of a-sulfofatty esters (e.g. of about 10 to carbon atoms, such as methyl asulfomyristate or a-sulfotallowate).
• alpha olefins and bisulfites e.g. sodium bisulfite
• primary paraffin sulfonates of about 10 20, preferably about 15-20, carbon atoms
• sulfates of higher alcohols e.g. salts of a-sulfofatty esters (e.g. of about 10 to carbon atoms, such as methyl asulfomyristate or a-sulfotallowate).
• sulfates of higher alcohols are sodium lauryl sulfate, sodium tallow alcohol sulfate. Turkey Red Oil or other sulfated oils, or sulfates of monoor digly-cerides of fatty acids (e.g.
• alkyl poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having one to five ethenoxy groups per molecule); lauryl or other higher alkyl glyceryl ether sulfonates; aromatic poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually hav- 19 ing one to 20 oxyethylene groups per molecule preferably two-l2).
• the suitable anionic detergents include also the acyl sarcosinates (e.g. sodium lauroylsarcosinate) the acyl esters (e.g. oleic acid ester) of isethionates, and the acyl N-meth-yltaurides (e.g. potassium N-methyl lauroylor oleyl tauride).
• acyl sarcosinates e.g. sodium lauroylsarcosinate
• the acyl esters e.g. oleic acid ester
• acyl N-meth-yltaurides e.g. potassium N-methyl lauroylor oleyl tauride
• the most highly preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium (such as, mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates.
• alkali metal such as sodium and potassium
• alkaline earth metal such as calcium and magnesium
• the particular salt will be suitably selected depending upon the particular formulation and proportions therein.
• Nonionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.
• nonionic surface active agents which may be used theremay be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about six to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannitan monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide.
• Cationic surface active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and as quaternary groups.
• suitable synthetic cationic detergents there may be noted the diamines such as those of the type RNI-lCJ-LNl-l wherein R is an alkyl group of about 12 to 22 carbon atoms, such as N-2-aminoethyl stearyl amine and N-2- aminoethyl myristyl amine; amide-linked amines such as those of the type RCONHC l-L,Nl-l wherein R is an alkyl group of about nine to 20 carbon atoms, such as N-2-amino ethylstearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to 18 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain one to three carbon atoms, including such one to three carbon alkyl groups bearing inert subsituents, such
• Typical quaternary ammonium detergents are ethyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl dilauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding methosulfates and acetates.
• amphoteric detergents are those containing both an anionic and a cationic group and a hydrophobic organic group, which is advantageously a higher aliphatic radical, e.g. of l0-20 carbon atoms.
• suitable amphoteric detergents are those containing both an anionic and a cationic group and a hydrophobic organic group, which is advantageously a higher aliphatic radical, e.g. of l0-20 carbon atoms.
• these are the N- long chain alkyl aminocarboxylic acids (e.g. of the formula RN R'-O O OM) the N-long chain alkyl irninodicarboxylic acids (e.g. of the formula RN(RCOOM) and the N-long chain alkyl betaines (e.g. of the formula R] RNR C O O) where R is a long chain alkyl group, e.g.
• R is a divalent radical joining the amino and carboxy portions of an amino acid (e.g. an alkylene radical of one-four carbon atoms)
• M is hydrogen or a salt-forming metal
• R is a hydrogen or another monovalent substituent (e.g. methyl or other lower alkyl)
• R and R are monovalent substituents joined to the nitrogen by carbon-to-nitrogen bonds (e.g. methyl or other lower alkyl substituents).
• amphoteric detergents are N-alkyl-beta-amino-propionic acid; N-alkyl-beta-iminodipropionic acid, and N-alkyl, N,N- dimethyl gylcine; the alkyl group may be, for example, that derived from coco fatty alcohol, lauryl alcohol, myristal alcohol (or a lauryl-myristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols.
• the substituted aminopropionic and iminodipropionic acids are often supplied in the sodium or other salt forms, which may likewise be used in the practice of this invention.
• amphoteric detergents examples include the fatty imidazolines such as those made by reacting a long chain fatty acid (e.g. of to carbon atoms) with diethylene triamine and monohalocarboyxlic acids having two to six carbon atoms, e.g. l-coco-S-hydroxyethyl-5-carboxymethylimidazoline; betaines containing a sulfonic group instead of the carboxylic group; betaines in which the long chain substituent is joined to the carboxylic group without an intervening nitrogen atom, e.g. inner salts of 2- trimethylamino fatty acids such as Z-trimethylamino-lauric acid, and compounds of any of the previously mentioned types but in which the nitrogen atom is replaced by phosphorus.
• a long chain fatty acid e.g. of to carbon atoms
• diethylene triamine and monohalocarboyxlic acids having two to six carbon atoms, e.g. l-coco-S-hydroxy
• the detergent composition may further contain one or more water-soluble builder salts which may be either organic or inorganic in nature. Suitable representatives include the following:
• Borax Ethylene diamine tetraacetic acid tetrasodium salts
• Nitrilotriacetic acid tri sodium salt etc.
• Mixtures of two or more inorganic or organic salts can be used, as can mixtures of inorganic and organic salts.
• water-soluble, alkali metal polyphosphate builder salts are particularly preferred herein. These salts form water-soluble complexes with calcium and magnesium ions found in hard water and thereby prevent the formation of insoluble salts which tend to deposit upon textiles during a washing cycle. Further, such phosphates enhance the detersive efficiency of anionic detergents, aid in controlling sudsing powers and aid in keeping soil suspended in the washing bath after its removal from the soiled textiles.
• compositions of the invention may be included in compositions of the invention, whether in solid or liquid form, by addition in known manner to the aqueous mixtures or to the solidified product.
• higher fatty acid amides such as coconut or lauric monoethanolamide, isopropanolamide and the like
• hydrotropic solubilizing agents such as xylene or toluene sulfonates
• organic solubilizing agents such as ethanol, ethylene glycol and hexylene glycol
• sodium carboxymethylcellulose and polyvinyl alcohol antiredeposition agents optical and fluorescent brightener materials
• coloring agents corrosion inhibiting agents; germicides; perfumes; a bluing agents; and the like.
• Preferred compositions advantageously contain a hydrophobic colloidal cellulosic soil-suspending agent which is soluble or dispersible in water also.
• the joint use of the combination of the cellulosic compound and polyvinyl alcohol is particularly effective for soil-suspension properties during the washing of a variety of fabrics, including both cotton and synthetic fibers such as nylon, Dacron and resin-treated cottons.
• the mixtures is used preferably in a total amount of 0.1 to 2 percent by weight of the solids.
• Preferred cellulosic compounds are the alkali metal salts of a carboxy lower alkyl cellulose having up to three carbons in the alkyl group, such as the sodium and potassium salt of carboxymethylcellulose. Suitable salts are sodium carboxyethylcellulose; the cellulose sulfates and lower alkyl and hydroxyalkylcellulose ethers such as methyl-, ethyl-, and hydroxyethylcellulose.
• the proportions of such ingredients are not particularly critical and may be selected so as to conform with established practice.
• the detergent agent is usually employed in concentrations ranging from about 2 to about 50 percent by weight of the composition.
• the builder salts, whether organic or inorganic, are preferably employed in concentrations ranging from about 10 to about percent by weight of the composition.
• Other ingredients of a conventional nature include perfume and chelating agents.
• the desired pH level may be readily achieved by the addition of suitable bufi'ering agents to the bleaching composition, the latter being provided either as a solution or a dry powder, granules, flakes, etc.
• the bleaching composition may be effectively used at relatively high pH values thereby permitting the conjunctive use of common household laundry soaps as well as detergents specifically devised for preventive bleaching of fiber materials.
• a chelating agent as, for example, the sodium salts of diethylenetramine pentaacetic acid, ethylene diamine tetraacetic acid, etc. and/or magnesium silicate.
• a pH within range of from about 6-10 is recommended.
• a bleaching composition consisting essentially of a solid, stable inorganic peroxygen compound and a water soluble N- m-halobenzoyl imide selected from the group consisting of N- m-halobenzoyl succinimide and N-m-halobenzoyl hydantoin and where said halo is selected from the group consisting of bromo and chloro, the mole ratio of said peroxygen compound to said imide being from about 0.5: 1 to about 6: l.
• composition according to claim 1 wherein said halo is chloro.
• a composition according to claim 1 wherein said imide compound is N-m-chlorobenzoyl 5,5-dimethyl hydantoin, the peroxygen compound is sodium perborate and the ratio of said perborate to said hydantoin compound is at least 2: l.
• composition according to claim 1 wherein said imide compound is N-m-chlorobenzoylsuccinimide.
• composition according to claim 1 wherein said imide compound is N-m-chlorobenzoyl-S ,S-dimethylhydantoin.
• composition according to claim 1, wherein said peroxygen compound is sodium perborate.
• composition according to claim 1 further containing an organic synthetic detergent in amounts ranging from about 2 percent to 50 percent by weight of composition.
• composition according to claim 1 wherein the mole ratio of said peroxygen compound to activator is up to about 2:1.
• a process for bleaching which comprises contacting the material to be bleached with an aqueous solution containing the composition claimed in claim 1.
• a composition according to claim 3 including from 2 to 50 percent by weight of an organic synthetic detergent.

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

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Citations (5)

• 1968
  • 1968-10-11 DE DE19681802576 patent/DE1802576A1/de active Pending
  • 1968-10-15 CH CH1542068A patent/CH489658A/de not_active IP Right Cessation
  • 1968-10-28 GB GB50993/68A patent/GB1247857A/en not_active Expired
  • 1968-10-30 FR FR1590335D patent/FR1590335A/fr not_active Expired
  • 1968-10-31 BE BE723233D patent/BE723233A/xx unknown
• 1971
  • 1971-01-11 US US105653A patent/US3655567A/en not_active Expired - Lifetime

Patent Citations (5)

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