US3681275A

US3681275A - Acrylonitrile composition improved in yellowness and brightness and production of fibers therefrom

Info

Publication number: US3681275A
Application number: US3317A
Authority: US
Inventors: Kenji Takeya; Hideto Sekiguchi; Kunio Tanahashi; Junji Tsuge
Original assignee: Japan Exlan Co Ltd
Current assignee: Japan Exlan Co Ltd
Priority date: 1969-01-27
Filing date: 1970-01-16
Publication date: 1972-08-01
Anticipated expiration: 1989-08-01
Also published as: GB1256445A; NL7000778A; ES375685A1; DE2003383A1; FR2029457A1; DE2003383C3; BE744916A

Abstract

ACRYLONITRILE FIBERS IMPROVED IN YELLOWNESS AND BRIGHTNESS ARE OBTAINED BY INCLUDING THEREIN A MONOESTER OF GLYCERIN WITH A HIGHER FATTY ACID OR A DERIVATIVE OF ITS MONOESTER.

Description

Aug. 1, 1972 KENJQI TAKEYA ETAL 3,681,275

ACRYLONITRILE COMPOSITION IMPROVED IN YELLOWNESS AND BRIGHTNESS AND PRODUCTION OF FIBERS THEREFROM Filed Jan. 16, 1970 Brightness Content of glyceryl monostearate in fiber Content of glyceryl monoatearate in fiber Attorneys United States Pa tent O 1 Int. Cl. C08f 3/7 6; D06m 13/10 U.S. Cl. 260-23 R 9 Claims ABSTRACT OF THE DISCLOSURE Acrylonitrile fibers improved in yellowness and brightness are obtained by includingtherein a monoester of glycerin with a higher fatty acid or a derivative of its monoester.

This invention'relates to an acrylic fiber improved'in the yellowness and brightness, and more particularly to an acrylic fiber containing a monoester of glycerin with a higher fatty acid or a derivative of its monoester, and improved in the yellowness and "brightness. This invention also. relates to a composition for producing such improved acrylic fibers.

An improvement in the yellowness and brightness of an acrylic fiber means an improvement in the whiteness and brightness of said fiber. It is important to improve these properties in elevating the commodity 'value of acrylonitrile fibers. Thus, the improvement in the whiteness and brightness of an acrylonitrile fiber is an essential condition for imparting to the fiber the inherent color of a dye used in dyeing said fiber. Further, the higher the,

whiteness and brightness of said fiber, the brighter the tone of the fiber dyed in a light color and the higher the commodity value of the dyed product.

Various treating methods for improving the whiteness and brightness of acrylonitrile fibers have heretofore been suggested. However, most of the conventional methods require special treatments andare difficult to industrially put into practice. Further the whiteness and brightness of the treated fibers have been not fully satisfactory.

A main object of the present invention is to provide an acrylonitrile fiber having an improved tone characteristic.

Another object of the present invention is to provide an acrylonitrile fiber highly improved in the yellowness and brightness, and excellent in the dyeing characteristic.

A still further object of this invention is to provide. a homogeneous solution which isv capable of beingspun into acrylic fibers having improved yellowness and brightness.

Other objects of this invention will become apparent fromthe following description. p

The above mentioned objects of this invention are accomplished by providing a homogeneous spinning solution which comprises an acrylonitrile polymer, an inert solvent for said polymer, and from 0.2% to 20% by weight (based on the weight of said polymer) of a monoglyceride or its derivative having the general formula (I):

wherein R is an alkyl or alkenyl group containing to 22 carbon atoms, and each of m and n is an integeri'sat- 3,681,275 Patented Aug. 1, 1972 .isfying the formula 0m+nl0. The spinning solution may be extruded through orifices of a spinneret to form fibers in a conventional manner.

When about 1 to 15% by weight (based on the polymer) of the compound represented by the above general Formula I is present in a spinning solution, optimum results of the improved yellowness and brightness will be given. to the fiber formed from said spinning solution. The use of more than 20% by weight of the compound (I) tends to deteriorate such other properties of the fiher as the tenacity, Youngs modulus and wet-tenacity.

Such acrylonitrile fiber containing the compound representedby the General Formula I of the present invention is far higher in the yellowness and brightness than conventional acrylonitrile fiber. Therefore, even if the fiber of the present invention and the conventional fiber are compared with each other with the naked eye, the fiber of the present invention will be found to be remarkably brighter. Further, whereas the conventional acrylic fiber is somewhat yellowish, the acrylic fiber of the present invention has a snow-whiteness. Therefore, in the .dyeing of the fiber obtained according to the present inin a light color, there will be obtained a dyed product having a very bright tone.

Further, the compound represented by the General Formula I has a plasticizing effect in the acrylic fiber. It is therefore possible to practically dye such fibers containing said compound at such low temperature as below 100 C. or particularly at about to C. Thus, owing to the plasticizing effect of the compound having the General Formula I, the permeation of the dye into the acrylonitrile fiber will be made easy and, therefore, even at a low temperature, the dye can be absorbed in the fiber to a sufficient extent. Such low temperature dyeing is advantageous to keep a desired hand peculiar to acrylonitrile fibers. On the other hand, in the conventional boiling dyeing, there has been a disadvantage that utmost care must be taken by using a special technique in order to retain said hand. Thus the acrylonitrile fiber of the present invention is fareasier to dye than conventional acrylonitrile fiber.

As compounds represented by the General Formula I, there can be enumerated, for example, a monoester of glycerin with lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid or behenic acid and its ethylene oxide additives; a monoester of glycerin with myristoleic acid, palmitoleic acid, petroselinic acid, vaccenic acid, oleic acid, linoleic acid, linolenc acid, elaidic acid, eleostearic acid, parinaric acid, gadoleic acid or arachidonic acid and its ethylene oxide additives.

According to the present invention, by extruding a homogeneous spinning solution containing from about 5 to about by weight of an acrylonitrile polymer consisting mainly of acrylonitrile, a compound represented by the above General Formula I in an amount of 0.2 to 20% by weight based on the Weight of said polymer, and an inert solvent for said polymer, a fiber highly improved in the yellowness andbrightness can be produced. The spinning can be conducted in a manner known per se.

The compound represented by the above General Formula I of the present invention can be added before, simultaneously with or after the addition of the solvent in preparing the spinning solution. The acrylonitrile polymer can be produced by suc conventional process (e.g. U.S. Pats. Nos. 2,751,374,

3,202,641, 2,748,106, 2,777,832 and 2,628,223). Then a homogeneous solution containing from about 5 to about 35% by weight of said polymer in an inert solvent is pre- 3 pared. Any known inorganic or organic solvent inert to the acrylonitrile polymer can be used. The spinning solution of the present invention is spun into fibers by a generally known wet-spinning or dry-spinning process. As described above, in practising the present invention, it is possible to use either of inorganic and organic solvents. Particularly, when an inorganic solvent such a concentrated aqueous solution of a metal halide, thiocyanate and those salts and mixed salts mentioned in U.S. Pats. No. 2,648,646 through 2,648,649 is used, the efiect of the present invention will be increased. Examples of the metal halides and thiocyanates are zinc chloride, calcium chloride, lithium bromide, cadmium bromide, cadmium iodide, sodium thiocyanate, calcium thiocyanate, potassium thiocyanate, zinc thiocyanate, ammonium thiocyanate, etc.

The acrylonitrile polymer consisting mainlyof acrylonitrile is a homopolymer of acrylonitrile or a copolymer of at least 70%, preferably at least 80% by weight of acrylonitrile and up to 30%, preferably up to by weight of at least one monoethylenically unsaturated monomers copolymerizable with acrylonitrile. Such monoethylenically unsaturated monomers include acrylic acid; methacrylic acid; such acrylic esters as ethyl acrylate, methyl acrylate, butyl acrylate, octyl acrylate, methoxyethyl acrylate, phenyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and dimethyl aminoethyl acrylate; such methacrylic esters as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methoxyethyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and hydroxyethyl methacrylate, hydroxypropyl methacrylate and dirnethyl aminoethyl methacrylate; acrylic amides and methacrylic amides or their alkyl substituents; such unsaturated ketones as methyl vinyl ketone, phenyl vinyl ketone and methyl isopropenyl ketone; such vinyl esters of organic carboxylic compounds as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl thiolacetate and vinyl benzoate; N-alkylmaleinimide, N-vinyl carbazole, N-vinyl succinimide, N-vinyl phthalimide, N-vinyl pyrrolidone and vinyl ether; such vinyl pyridines as 2- vinyl pyridine, 4-vinyl pyridine and Z-methyl-S-viuyl pyridine; styrene and its alkyl substituents; allyl alcohol; such vinyl halides and vinylidene halides as vinyl chloride, vinyl bromide and vinylidene chloride; methacrylonitrile; such unsaturated sulfonic acids as allylsulfonic acid, methallylsulfonic acid and styrene sulfonic acid and their salts; such cyclic compounds as betapropiolactone.

Preferably the polymers have an average molecular weight of 40,000 to 150,000, although a molecular weight may range from 15,000 to 250,000.

The invention will be further explained by referring to the following examples and to the accompanying drawings wherein FIG. 1 and FIG. 2.are graphs respectively showing the brightness and yellowness of acrylonitrile fiber in relation to the glyceryl monostearate content in the fiber. In these examples, all percentages and parts are by weight unless otherwise specified.

EXAMPLE 1 Eleven parts of an acrylonitrile polymer consisting of 91.0% acrylonitrile, 8.6% methylacrylate and 0.4% sodium methallyl sulfonate, produced by an aqueous suspension polymerization process with a sodium chloratesodium sulfite redox catalyst system, were dissolved in 89 parts of a 44.3% aqueous solution of sodium thiocyanate to prepare a homogeneous polymer solution. Then, each of monoester compounds of glycerin with higher fatty acids mentioned in Table 1 was added and mixed. The thus obtained spinning solution was extruded into a 12% aqueous solution of sodium thiocyanate at 3 C. through a nozzle of 15,000 orifices of an orifice diameter of 0.067 mm. to form filaments. The filaments were washed with water, then treated for 15 seconds in an aqueous solution of a pH of 3 containing 0.03% Na SO and then stretched 10 times the length in boiling water. Then the'stretched filaments were wet-heat-relaxed at a temperature of 125 C. so as to shrink by about 30% to make fibers of 3 deniers. The yellowness and brightness of the thus obtained acrylonitrile fibers were measured and the results are shown in Table 1.

Measurement of yellowness The fibers were arranged in the same direction, and the reflection factors against lights of wave lengths of 453, 553 and 595 m were determined on the basis of a magnesium oxide plate and the yellowness was calculated by the following formula. -It is shown that, the smaller the value, the lower the colored degree of the fiber.

Yellowness M Measurement of brightness TABLE 1 ssa Y n B i a i on e owr ht- Additive (percent) ness r less No addition 0 5.2 88.4 GMS 3 3.3 91.2 5 2.7 92.0 5 2.9 92.4 5 3.8 90.8 5 3.2 91.9 '5 7 3,5 91.2

1 Based on the weight of the polymer.

'In the above table, GMS represents glyceryl'monostearate, GMS (POE-2) or GMS (POE-6) represents an additive of 2' or 6 mols of ethylene oxide to glyceryl monostearate, GMO represents glyceryl mono-oleate and GML represents glyceryl monolaurate.

EXAMPLE 2,

In the same manner as in Example 1, a homogeneous? solution of an acrylonitrile polymer with an aqueous solution of sodium thiocyanate was prepared. Into said poly- I, mer solution was added and mixed glyc'erylmonostearate at each of such rates as shown in Table 2. The thus obtained spinning solution was wet-spun according to Example 1 and was then after-treated to obtain an acrylonitrile fiber of 3 deniers. The yellowness and brightness of each of the thus obtained acrylonitrile fibers were lowness and brightness were remarkably improved. When acrylonitrile fibers showing a difference of more than about 1 in each'ot the values or the yellowness and brightness were compared with each other, a definite difference between them was seen distinctly with the naked eye. That is to say, when the acrylonitrile fiber'containing 2.8% glyceryl monostearate in this example and a blank acrylonitrile fiber containing no glyceryl monostearate at all were observed with the naked eye, the blank fiber was rather yellowish and had a rather dull pastel-like luster but the fiber containing the compound according to the present invention showed no yellowing at all, had a snowwhiteness, was never dull, had no pastel-like luster and was clear. H t

As apparent from Table 2, the compound represented by the General Formula I according to the present invention'and the acrylonitrile polymer are so highin the compatibility that the holdabilit'y of said compound in the fiber is high. (The drop of said compound is little in the spinning, water-washing and after-treating steps.)

TABLE 2 Content in Amount of addition to spinning the fiber 1 Yellowsolution 1 (percent) (percent) ness Brightness N addition 4. 9 88. 0.8 0. 6 4. 1 89. 5 1. 8 3. 7 90. 4 2. 8 3. 0 90. 8 3. 8 2. 9 91. 5 4. 7 2. 7 91. 8 6. 7 2. 6 91. 8 8. 5 2. 4 92. 0

1 Based on the weight of the polymer. 9 Based on the weight of the fiber.

What we claim is:

1. As a new composition of matter a homogeneous spinning solution comprising an acrylonitrile polymer selected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70% of acrylonitrile and up to 30% by weight of at least one monoethylenically unsaturated monomer copolymerized therewith, an inert solvent for said polymer, and from 0.2% to 20% based on the weight of said polymer of a mono-glyceride or its derivative having the general formula wherein R is an alkyl or alkenyl group containing 10 to 22 carbon atoms and each of m and n is an integer satisfying a range of Om-l-n l0.

2. The composition of claim 1 wherein said solution contains from about 5% to about 35% by weight of said polymer.

3. The composition of claim 1 wherein said solution contains from 1% to by weight of said mono-glyceride or its derivative.

4. The composition of claim 1 wherein said mono glyceride is glyceryl monostearate.

5. The composition of claim 1 in which said polymer contains at least 80% acrylonitrile by weight in polymerized form.

6. The composition of claim 1 wherein said solvent is inorganic solvent for the acrylonitrile polymer.

7. The composition of claim 6 wherein said inorganic solvent is a concentrated aqueous solution of sodium thiocyanate.

8. A process for preparing filaments improved in the yellowness and brightness which comprises extending a 6 homogeneous solution comprising from about 5% to about 35% by weight of a polymer containing at least acrylonitrile in polymerized form, an inert solvent for said polymer, and from 0.2% to 20% based on the weight of said polymer of a mono-glyceride or its derivative having the general formula wherein R is an alkyl or alkenyl group containing 10 to 22 carbon atoms and each of m and n is an integer satisfying a range of 0m+nl0, through spinning orifices to form filaments, washing said filaments in an aqueous bath whereby said solvent is substantially removed from said filaments, and thereafter drying said filaments.

9. A filament comprising an acrylonitrile polymer selected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70% acrylonitrile and up to 30% of at least one monoethylenically unsaturated monomer copolymerized therewith having included therein from 1% to 15% by weight of a monoglyceride or its derivative having the general formula wherein R is an alkyl or alkenyl group containing 10 to 22 carbon atoms and each of m and n is an integer satisfying a range of 0m+n10.

References Cited UNITED STATES PATENTS 3,451,140 6/1969 Nakagawa et al. 264-482 3,578,621 5/1971 Stapfer 26031.6 3,047,521 7/ 1962 Harman 26023 3,113,369 12/1963 Barrett et al. 8130.l 3,410,819 11/1968 Kourtz et al. 26029.6 3,479,308 11/ 1969 Gattenby et a1. 26023 DONALD E. CZAJA, Primary Examiner R. W. GRIFFIN, Assistant Examiner US. Cl. X.R.

8-130.l; 26023 AR, 23 S, 23 XA, 29.6 AB, 30.8 R, 31.4 R, 31.6, 88.7 B; 264-482