Патент USA US2134001код для вставки
Patented 0'... 25, ‘1938 . UNITED STATES » PAT: 2.134.001 Momnoomm- mm.‘ _ t. v. . _ N Lindley pany, Mich.,E. Midland, assignors Mills and Mich., toWilliam The a corporation Dow w. Ohemical"Com-' Allen, of Midland,_Michi- '-: - _ "" ' ; gan , No Drawing. Serial Application No. 169,470 October-v16, 1.4937,:v 1 _ ' - 6 Claims. (Q1. 21-5) This invention relates to the'protection of fur, mothproo?ng of woolen- fabrics and the like, the hair, feathers, wool, etc., against the attack of articles so treated are not stained or attacked moths. It is more particularly concerned with ' thereby orcaused todevelop any distinctive odor. the mothproo?ng of fabrics. _ ‘Furthermore, these aryloxy alkylols are not ap-, Some agents heretofore employed for moth preciably dissipated from the fabric impregnated 5 proo?ng are capable of attacking or staining the therewith by contacting such fabric with water, treated material. Other mothproo?ng products ‘ soap solutions, or petroleum distillate dry-clean are highly volatile and impermanent in nature ing ?uids, or by volatilization or ‘sublimation, of and are soon dissipated by vaporization from the 10 material to which they are applied. Temporary protection has also been afforded by compounds which are soluble in water or soap solutions.‘ the compound. ' . , . The aryloxy alkylols are, for the most part, 10 odorless, water-white, viscous likuids. These compounds may he prepared by reacting a suit Some protecting agents such as the phenols and ' able phenol with a halo alcohol,v e. g., ethylene mercury and ?uorine compounds are irritating bromohydrin, propylene chlorhydrin, mono-~ 15 to the skin and poisonous to human beings, while > chlorobutanol, etc.,- in the presence of a suitable 15 other common organic derivatives are objection alkali, e. g., NaOH, KOH, etc. 'I'hesecompounds' able because of their characteristic odor. A fur may be dissolved in suitable solventsv inamounts , ther disadvantage in the use of many of the com ranging between 1.0 and l0per cent by weight ' mon mothproo?ng compositions is the fact that thereof and advantageously employed as- moth-g 20 the residues deposited in the treated article fol proo?ng compositions. ' We have ‘found that so- 20 lowing evaporation of liquid constituents are lutions containing between about 3 and about 7-5. '_ , crystalline and are soon dusted out of material per cent by weight of such compounds'are‘satis treated therewith. Among the objects of this invention is to pro 25 vide a method for the protection of the afore mentioned materials which will (1) give rela tively permanent protection therefor against at tack by moths, and (2) yield a protected product free from objectionable odor and toxicity to hu so mans. Another object is to provide a vcomposi tion comprising a volatile organic solvent having dissolved therein a mothproo?ng material which upon application to material susceptible to attack will prevent destruction thereof by moths without 85 at the same time staining or otherwise injuring the material. ‘‘ We have discovered that the foregoing advan tages can be obtained by employing as mothproof ing agents aryloxy alkylols having the formula 40 factory. I - _, ' In the numerous tests carried out‘toe'stablish ' the utility of the aryloxy alkylols as mothproof- >25 ing agents, the larvae of the black carpet beetle (Attagenus piceus) were employed. This insect > is a common household pest attacking woolens, furs, and other materials' It is particularly de structive to fabrics used in upholstered furniture 30 and to woolen carpets and rugs. It is more resist ant and harder to control than the common case' making clothes moth or tapestry moth, and con-' centrations of ‘ material found suitable for its control on fabrics have been shown to be more _ than adequate for the control of the latter species. The following examples are illustrative of cer tain modes in which our invention may be. ap plied, but are not to be construed as limiting the same. ' 40 Example 1 A‘number of samples of‘ white wool mohair], cloth were saturated with solutions of 4-tertiary- > butyl phenoxy ethanol in a volatile, highly refined petroleum distillate, thereafter pressed to remove 45 . wherein R represents an alkyl residue and X rep resents a hydrocarbon substituent containing at least 4 carbon atoms and selected from the group consisting of the alkyl and cycloalkyl radicals. 50 When compounds of the above class, or. mixtures thereof, are incorporated with a suitable organic solvent and particularly with a lower aliphatic alcohol, a liquid chlorinated hydrocarbon, or a volatile, highly re?ned petroleum fraction, and the solution so formed thereafter employed in the excesses of the treating ?uid, and allowed to dry. On each of a number of these samples ?ve larvae of the black carpet beetle were placed and the sample‘ folded over the larvae. .These infested cloth samples were placed in a closed ‘cardboard 50 ’ box and examined from time to time to determine the amount of feeding or other attack directly attributable to the beetle larvae. Simultaneous tests were made with larvae upon untreated sam ples of the mohair, both control and test samples 55 " 2,134,001 2 being thereafter incubated at temperatures of 85°-90° F. and at a ‘relative humidity of 70-75 per cent. Examination of incubated samples impregnated with a 3 per cent 4-tertiary-butyl phenoxy ethanol solution showed that after three Other solvents for the aryloxy alblols, form-, ing solutions which may be employed as dry cleaning agents, are liquid halogenated hydrocar bon compounds such as carbon tetrachloride, chloroform, ethylene chloride, trichloro-ethylene, the impregnated samples. In the case of the samples originally impregnated with a 5 per cent solution of the treating compound, there was no‘ feeding by the larvae after three weeks incuba chlorobenzene, and the like; hydrocarbon com pounds, such as benzene, the lower paramn hy drocarbons, toluene, and the like; and the alco hols, such as ethyl and methyl alcohol, etc. Per, fumes, coloring agents, and the like, may be in 10 corporated in the mothproo?ng ?uid, if desired. tion and an average of between 2 and 3 of the lar vae were'dead on each test sample. The un in a water-immiscible solvent, such composition weeks there had been no feeding by the larvae. An average of two larvae were dead on each of When the aryloxy alkylcl compound is dissolved treated controls showed a slight feeding by the , may be employed as an emulsion with a soap or other wetting or emulsifying agent and water. 15 Any of the cleansing agents and detergents com two weeks, and heavy feeding at the end of three weeks incubation. Tests carried out over the mon to‘ the cleaning art may then be employed same period upon mohair treated by immersion in conjunction therewith. We claim: in the petroleum distillate alone showed moderate 1. A process for mothproo?ng woolen fabrics 20 feeding by the larvae after one week, moderate ‘ and other materials subject to attack by moths feeding after two weeks, and heavy feeding at‘ which comprises treating such material with an the end of a three-week period. 15 larvae after one week, moderate feeding after Example 2 26 aryloxy alkylol compound having the formula ' Samples of the impregnated mohair described in the foregoing example were thoroughly dried and subsequently immersed and well- washed in an excess of a common-home dry-cleaning ?uid. These samples were thereafter dried andexposed to carpet beetle larvae as described in Example 1. wherein R represents an alkyl residue and X 30 represents a hydrocarbon substituent containing No feeding was shown after two weeks incuba tion of the mohair samples orlginallyimpreg . at least 4 carbon atoms and selected from the nated with 3 and 5 per cent a-tertiary-butyl group consisting of the alkyl and cycloalkyl phenoxy ethanol solutions. radicals. 2. A process for mothproo?ng woolen fabrics Example 3 , and other materials subject to attack by moths Dried samples of the impregnated woolen mo which comprises treating such material with 4 hair were thoroughly washed in a 0.5 per cent so- , lution of Ivory soap in water at a temperature of 40° C. After 20 minutes contact with'the soap 40 solution, these test samples were rinsed in run ning water, and dried. It was found that upon infestation with the carpet beetle and two weeks incubation the samples originally impregnated with 5 per cent of i-tertiary-butyi phenoxy 45 ethanol were substantially free from injury. In the foregoing examples no staining of the impregnated cloth was observed and the fabric itself was not damaged by the aryloxy alkylol compound. The impregnated cloth in each in stance was odorless, and even after prolonged weathering showed no discoloration. The pre servative showed no tendency to crystallize out or to volatilize, from the fabric nor was the fabric greasy or oily to the touch. 55 Among other aryloxy alnlol compounds which may be similarly employed for the protection of fabrics and the like against attack by moths are: 2-tertiary-butyl phenoxy ethanol, 3-tertiary amyl phenoxy ethanol, 4-normal-butyl phenoxy ethanol, 3-secondary-amyl phenoxy ethanol, 4 secondary-butyl phenoxy propanol,~ il-normal-amyl phenoxy propanol, 2-normal-hen1 phenoxy pro panol, i-tertiary-butyl phenoxy butanol, 2-cyclo hexyl phenoxy ethanol, i-cyclohexyl phenoxy ethanol, 2-cyclopentyl phenoxy ethanol, 3-cyclo hexyl phenoxy propanol, i-cyclohex'yl phenoxy propanol, 2-cyclohexyl phenoxy butanol, etc. . tertiary-butyl phenom’ ethanol. 3. A process for mothproo?ng woolen fabrics and other materials subject to attack by moths 40 which comprises treating such materials with a composition comprising a-tertiary-butyl phenoxy ethanol dissolved in an organic solvent. 4. A process for mothproo?ng woolen fabrics and other materials subject to attack by moths 45 which comprises treating such materials with a composition comprising i-tertiary-butyl phenom ethanol dissolved in a light petroleum distillate. 5. A composition consisting of material liable to attack by moths having incorporated therein an aryloxy alkylol compound having the formula wherein R represents an alLvl residue and X rep resents a hydrocarbon substltuent containing at least 4 carbon atoms and selected from the group consisting of the alkyl and cylcloalkyl radicals. 6. A composition consisting of material liable to attack by moths having incorporated therein 4-tertiary-butyl phenoxy ethanol. ‘ ' WILLIAM W. ALLEN.