Patent GB-392191-A (GB)
Title: Manufacture and treatment of artificial filaments, threads, yarns, ribbons, fabrics and the like containing cellulose derivatives
IPC: C08K5/16
Filed: 1931-11-05
Abstract: Cyclic ethers obtainable by the condensation of aliphatic compounds containing at least four hydroxyl groups with glycols, aldehydes, or ketones, or ethers or esters of such cyclic ethers, are employed in the manufacture and treatment of artificial filaments, threads, yarns, ribbons, and the like containing cellulose derivatives, such compounds being used either as constituents of the solutions from which the products are formed, of the solutions, which may be of high concentration, in which they are coagulated, of swelling media therefor, in treatments such as dyeing, printing, stencilling, discharging, delustring, and relustring, as constituents of agents for improving the extension, pliability, or other properties of the filaments, threads, and the like, or as softening agents for use prior to stretching in the manufacture of filaments, threads, yarns, ribbons, fabrics, and the like.  The invention is particularly applicable in the manufacture of products from cellulose acetate, but it may also be applied in the case of products from other organic cellulose esters such as cellulose formate, propionate, butyrate, nitro-acetate of low nitrogen content, also cellulose nitrate, and ethers such as ethyl, butyl, or benzyl cellulose, mixed ethers, and mixed ether-esters, for example, oxy-ethyl cellulose acetate and ethyl cellulose acetate. Suitable aliphatic hydroxyl compounds are erythritol, sorbitol, mannitol, or other polyhydric alcohol containing not more than six hydroxyl groups.  These may be condensed with ethylene glycol, propylene glycol, 1, 2- or 2, 3-butylene glycol, isobutylene glycol, formaldehyde, acetaldehyde, acrolein, and acetone, and the condensation may be effected by any means, for example, those described in Specification 392,160.  Sulphuric acid, hydrochloric acid, phosphoric acid, zinc chloride, benzenesulphonic acid, calcium chloride, or similar agents may be used at low temperatures, but less powerful dehydrating agents may be used to effect the condensation at higher temperatures.  For example, a suspension of glucose or erythritol in acetone may be saturated with hydrogen chloride and allowed to stand until condensation occurs, the hydrochloric acid being removed by means of lead carbonate.  In cyclic ethers in which all the hydroxyl groups of the parent hydroxyl compound have not been etherified, these groups may either remain free, or be etherified or esterified with other radicles, for example, by methyl, ethyl, benzyl, acetyl, formyl, or lactyl groups. The ethers may be used in spinning solutions for artificial threads &c., whether by wet or dry methods.  They may further be employed in wet spinning processes, both in the actual coagulating baths, as described in Specifications 179,234, [Class 2 (ii), Cellulose &c.], 340,324, and 340,325, and in subsequent treatment baths as in Specifications 340,436 and 340,437.  In these applications, the compounds may be employed with other solvents and/or diluents, for example, acetone, methylacetone, methyl acetate, ethyl acetate, butyl acetate, ethers and esters of olefine and polyolefine glycols, for example, the monomethyl and ethyl ethers of ethylene and propylene glycols, glycol monoacetate, ethylglycol monoacetate and methylglycol monoacetate, methylene chloride, ethylene chloride, dichlorethylene, trichlorethylene, chloroform, methyl, ethyl, and other alcohols, hydrocarbons, and ethers, for example, isopropyl ether.  Acetaldehyde or other very low-boiling solvents may be used when it is desired to produce compounds having a high volatility.  In addition to low-boiling solvents and the cyclic ether compounds, medium or high-boiling solvents or plasticizers may also be employed, for example, triacetin, diethyl phthalate, dibutyl phthalate, sulphonamides, for example, alkylated xylene sulphonamides, sulphonanilides, tartrates, for instance dibutyl tartrate, diphenylol propane, triphenyl phosphate, and tricresyl phosphate, or other phenolic plasticisers.  Medium boiling solvents specified are ethyl lactate, diacetone alcohol, and tetrachlorethane.  Diluents, for example, benzene, toluene, xylene or other relatively cheap hydrocarbons or nonsolvents for the cellulose derivatives may be incorporated in the spinning solutions.  The cellulose derivative compositions may contain other constituents, for example, dyestuffs, pigments, fillers or resins, for example shellac, dammar, artificial resins of the phenolaldehyde type, and similar resins from other starting materials, for example, from diphenylol-propane and formaldehyde and other aldehydes, from urea or thiourea and formaldehyde, from glycerine or other polyhydric alcohol and phthalic acid or other polycarboxylic acid, and also the polymerized vinyl resins, for example, polymerized vinyl acetate.  The compositions may also include substances reducing flammability, for example, halogenated and particularly brominated organic compounds, for example, brominated acidylated amines, for example, tribrom-acetanilide.  When the cyclic ether compounds are used in the manufacture of artificial filaments, threads, yarns, ribbons, and the like they will in general be employed in conjunction with relatively low-boiling solvents, for example, acetone or mixtures of acetone with alcohol, or methylene chloride or ethylene chloride and alcohol. Fabrics containing cellulose derivatives may be treated with the cyclic ether compounds, for example, fabrics which have been delustred by moist steam or hot aqueous media may be relustred therewith.  The compounds may also be employed to diminish the tendency of woven fabrics to slip or warp or similar knitted fabrics to split or ladder, as described in Specification 280,990, [Class 2 (ii), Cellulose &c.]. Treatments with the ether compounds for improving the extension or pliability of filaments or threads of cellulose derivatives, and particularly for improving the knotting properties of thick filaments or artificial horsehair are mentioned. Such treatments are preferably carried out in the absence of tension or under light tension so that the materials can shrink, and are particularly important in relation to the treatment of filaments of low extension produced by wet spinning processes, or by the stretching of dry spun products, such shrinking processes being described in Specification 389,823.  The cyclic ether compounds may be employed in the production of sizes and the like to facilitate textile operations, and such size may contain other compounds such as polymerized vinyl compounds, oxidized linseed oil, or other drying oils.  The compounds may also be used for increasing the affinity of cellulose derivatives for dyeing, printing, discharging, loading, mordanting, and delustring compounds, so that the usual steaming or ageing treatment which it is customary to employ to fix the dyestuff or other agent in the material may be omitted.  As diluents for admixture with the cyclic ether compounds in the treatment of formed products containing cellulose derivatives, aliphatic, aromatic, or cycloaliphatic hydrocarbons, ethers, alcohols, or water may be employed.  According to one example, a solution of a condensation product of formaldehyde and erythritol is used as a coagulating bath in the spinning of filaments of cellulose acetate, the spinning solution also containing a small proportion of the condensation product, if desired.  According to another example, filaments or yarns of cellulose acetate are soaked in an alcoholic solution of a condensation product of acetone and erythritol before stretching. The Provisional Specification also describes the application of the cyclic ether compounds as softening agents for natural and artificial resins, including shellac, dammar, the phenol-aldehyde fusible soluble synthetic resins, and similar resins from other starting materials, for example, from diphenylolpropane and formaldehyde and other aldehydes, from urea or thiourea and formaldehyde, from glycerine or other polyhydric alcohol and phthalic acid or other polycarboxylic acid, and also the polymerized vinyl resins, for example polymerized vinyl acetate.  In addition to the Specifications mentioned above, Specifications 259,285, 277,089, 323,790, [all in Class 2 (ii), Cellulose &c.], 370,430, 371,461, and 392,186 also are referred to.ALSO:According to the Provisional Specification, cyclic ethers obtainable by the condensation of aliphatic compounds containing at least four hydroxyl groups with glycols, aldehydes, or ketones, or ethers or esters of such cyclic ethers, are employed as softening agents for synthetic resins, including the phenol-aldehyde fusible soluble synthetic resins, and similar resins from other starting materials, for example, from diphenylol propane and formaldehyde, from glycerine or other polyhydric alcohol and phthalic acid or other carboxylic acid, and also the polymerized vinyl resins, for example, polymerized vinyl acetate.