DE1289242B - Polypropylene fibers with improved dyeability - Google Patents

Description

The invention relates to polypropylene fibers with improved dyeability, the aluminum soaps contain.

Polypropylene fibers have, but can only, superior properties in several ways be colored with great difficulty. Because of this one has to a great extent endeavors to improve their dyeability. One has z. B. a wide variety of monomeric vinyl compounds Applied to the polypropylene by graft copolymerization, it has homogeneous mixtures made of polypropylene and a high molecular substance that has an affinity for dyes has, spun and has the polypropylene homogeneous with inorganic or organic salts, Oxides or hydroxides of metals mixed and then colored with dyes that are used to Capable of forming coordinative or ionic or salt-forming bonds with the metal are.

It is well known that fibers can be dyed in such a way that one can dye an inorganic one Introduces metal salt into the fibers, after which one dyes with the help of dyes that lead to training are capable of bonding with the metal. This dyeing process is known as "stain dyeing" known. As a result of the low affinity or compatibility of polypropylene with such Metal salts, however, this method cannot be applied to polypropylene. the Propylene fibers adsorb these metal salts from their aqueous solutions only to a very small extent Dimensions. Accordingly, this method results in only a weak coloration.

Even if these metal salts are mixed with the polypropylene and spun together with it getting good fibers is impossible because of poor tolerance as well because these mixtures are very difficult to spin. It is, however, possible, pretty much to get good fibers with pretty good dyeability when using the polypropylene for improvement the compatibility a metal salt of a higher aliphatic carboxylic acid mixed homogeneously and is spun (British Patent 932 897).

In the case of salts of higher aliphatic carboxylic acids, the molar ratio of aliphatic carboxylic acid radical to metal between 1: 1 and 3: 1, depending on on the valence number of the metal and the manufacturing conditions. When doing the above molar ratio is between 1: 1 and 2: 1, are at those valences of the metal that are not are associated with carboxylic acid residues. Hydroxyl groups. Such connections by the general formula

recognize colored spots as colored spots. By measuring the dye uptake, found that the effectiveness of the metal atoms in binding the dye is poor. Links, in which all valences are connected to carboxyl residues, show a superior compatibility, and no colored spots can be found on cross-sections of the colored fibers, from which it can be seen that uniform staining has taken place. However, since the relative The amount of metal, based on the molecular weight of the compound, is small, one has to use the Apply compound when mixing in large quantities, and in this case too, the dyeability is not big enough yet.

After it has been determined according to the invention that both the physical and the mechanical Properties as well as the dyeability of the fibers are improved by improving the compatibility polypropylene fibers have been found to have superior dyeability when they in addition to polypropylene 0.1 to 10 percent by weight of at least one compound of the general formula

(R, COO) _w Al (OR-i) "

RCOOAKOHk (RCOO) ₂ Al (OH)

are not satisfactorily compatible with polypropylene. When cross-sections of dyed fibers containing such a compound are observed under the microscope, the in Ri denotes an alkyl group having 7 to 29 carbon atoms and R-2 denotes an alkyl group having 1 to 18 carbon atoms, in and /; 1 or 2 and m + η = 3 are included.

The compounds of the general formula given above, in which the hydroxyl groups are replaced by alkoxy radicals, show an extremely good compatibility. On cross-sections of the colored No colored spots can be found on fibers.

If the dye uptake is measured, a very high level of dyeability is found. Since continue yourself Compounds in which the radical R2 of the abovementioned general formula is an alkyl radical with only 1 to 4 carbon atoms, sufficient Have compatibility, the relative amount of the metal, based on the molecular weight the connection, practically not reduced. Accordingly, it is not necessary to achieve to mix large amounts of this compound for higher dyeability.

If metal-containing compounds leak into the dyebath during dyeing, one takes place Combination of the dye with the metal atoms takes place. Because this combined product has no affinity compared to the polypropylene fibers, it means the loss of large amounts of dye. In addition, the leakage of the additives into the dyebath brings with it various other problems themselves. The compounds according to the invention show no such leakage into the dyebath. Even from this fact the superior compatibility of the compounds according to the invention can be seen.

Ri is an alkyl radical. The number of carbon atoms of Ri varies depending on the value of in and n.

It is in the range from 7 to 29, preferably from 7 to 17. In other words, compounds are preferred which are derivatives of carboxylic acids having 8 to 30, preferably 12 to 18, carbon atoms. If m = 2, the number of carbon atoms of Ri may be low. However, if m - 1 and the number of carbon atoms of Ri is small, sufficient compatibility can only be achieved if the number of carbon atoms is from

Ri is relatively large. In this case, however, the dyeability is poor. In comparison with the case where the number of carbon atoms of Ri is large and that of R-> is small, deep coloration is difficult to obtain.

R> is an alkyl radical. It is possible to increase the compatibility with the number of carbon atoms, which is 1 to 18, preferably 2 to 12. However, it is not preferable to unduly increase the compatibility by increasing the number of carbon atoms of R> because, as stated above, the dyeability is lowered in this case. Compounds in which m = 2 and η = 1, are compounds in which m = 1 and η = 2, superior in the dye affinity of the product.

The mixing ratio of the compounds of the general formula (I) in relation to the polypropylene varies depending on the values of Ri, Ri, in and / ;. In view of the mechanical properties and the dyeability of the fibers, the compounds are used in an amount of 0.1 to 10 percent by weight, preferably 1 to 5 percent by weight. When the mixing ratio is increased, the dyeability is improved and deep coloration can be obtained more easily, but the mechanical properties are deteriorated. On the other hand, if the mixing ratio is decreased, the mechanical properties improve, but sufficient dyeability cannot be obtained.

Examples of compounds of the above general formula which can be used according to the invention are, among other things, the stearoyloxy-diisopropoxy-aluminum, lauroyloxy-diisopropoxy-aluminum, stearoyloxy-dimethoxy-aluminum. the Stearoyloxy diethoxy aluminum, lauroyloxy diethoxy aluminum, the lauroyloxy-dilaiiroxy-aluminum, the distearoyloxy-monomethoxy-aluminum, the distearoyloxy-monoethoxy-aluminum, the disteaiOyloxy-monobutoxy-aluminum, the dilauroyloxy-monoisopropoxy-aluminum and the dioctoyloxy-monoisopropoxy-aluminum.

These compounds can be easily prepared by using a conventionally prepared Metal alkoxide with "a calculated amount of the carboxylic acid in question in an organic medium warmed up.

In the practice of the invention, it is possible to use a wide variety of stabilizers and other accessory center! as they are commonly used for polyolefins.

For dyeing the fibers according to the invention, those dyes which can be used in combination are capable of the aluminum atoms of the compounds according to the invention. Besides the usual Mordant dyes are dyes that have been developed for metal-containing polypropylene fibers, suitable.

Customary dyeing processes can be used for dyeing, and if necessary, by using of nonionic or anionic surface-active agents as dyeing auxiliaries Maintaining a pH value of 2 to 8 (for Weak acids are used to adjust the pH), by boiling and by dyeing Normal pressure it is possible to get beautiful and real colored products.

In making the dyeable polypropylene fibers of the invention, any of the usual ones can be used Melt spinning, wet spinning and dry spinning processes are used.

The following examples serve to further illustrate the invention.

example 1

27 parts by weight of aluminum powder, 300 parts by weight of anhydrous isopropyl alcohol and 0.5 part by weight of mercury (II) chloride were placed in a 2-1 flask given and heated. At the start of boiling were

5 2 parts by weight of carbon tetrachloride added. A violent reaction took place with the formation of hydrogen. The heating was about 5 hours continued, after which the reaction mixture was kept at a temperature of 70 ° C. overnight.

The insoluble substances were then allowed to settle. The supernatant was taking distilled at a pressure of 1 mm / Hg. The distillate passing over at a temperature of 125 to 132 C. winch collected, leaving about 190 g of triisopropoxyaluminum were obtained.

20.4 parts by weight of triisopropoxy aluminum and 28.4 parts by weight of stearic acid were in 200 parts by weight Benzene brought together and heated to the boiling point of benzene for 2 hours implemented. When the reaction mixture was added dropwise to ethanol, 40.6 parts by weight of stearoyloxydiisopropoxyaluminum became.

C ₁ THa ₅ COO • Al (OOHv) ₂

obtained in the form of easily crushable amorphous blocks. The substance did not show any sharp Melting point. Their softening point was about 200 C.

The stearoyloxy-diisopropoxy-aluminum (A) and crystalline polypropylene powder with an intrinsic Viscosity of 1.4, measured in tetralin at 135 C, were in the proportions given in Table I. mixed together and formed into tablets at a temperature of 220 ° C. Then was subjected to the usual melt spinning process and at a temperature of 130 ° C drawn to make fibers.

The fibers obtained were then rinsed, dyed and soaped under the following conditions: to get red colored fibers. The results of this treatment are summarized in Table I.

Wash:

Polyoxyethylene alkyl phenyl ether

0- (CH ₂ -CH ₂ O) _n H.

0.5 g / l

Sodium pyrophosphate: 0.1 g / l;

Ratio of fibers to rinsing liquid: 1:50;

Temperature: 70 ¹ C; Time: 30 minutes.

After the treatment, the fibers were washed with water.

To dye:

Soap:

CI Beizenrot 11 (C. 1:58 000), 3%, based on the fiber ^{weight (in the original: 3 0} / <) owf); a surfactant consisting mainly of a sodium alkylarylsulfonate: 1 g / l; Formic acid: 2% based on fiber weight (owf);

Ratio of fibers to liquid: 1:50. The temperature was raised within 30 minutes increased from 50 to 90 ° C and dyeing carried out for 90 minutes at this temperature, after which it was washed with water and soaped. Polyoxyethylene alkyl phenyl ether

- (CH ₂ -CH ₂ -O) _n H.

0.5 g / l

Sodium carbonate: 0.1 g / l
Ratio of fibers to liquid: 1:50; Temperature: 90 ° C; Time: 20 minutes. ■ After the treatment, the fibers were washed with water.

Table I.

No. Polypropylene Substance A Dry
tear resistance Dry
extensibility dye
recording Color fastness
opposite to .A-
Washfastness (Weight percent) (Weight percent) (S / den) <%) (%) sunlight 1 100 0 6.5 28.5 0 - - 2 99 1 6.4 27.0 65 5 5 3 98 2 6.5 25.8 71 6th 5 4th 97 3 6.2 26.4 73 6th 5 5 96 4th 6.4 28.0 75 6th 5

In this table, as well as in the following, the authenticity to sunlight was determined with the aid of the carbon arc process determined in accordance with Japanese Industrial Standards JIS-L 1044 (1959). The wash fastness was determined by the BC-2 cup method in accordance with JIS-L 1045 (1959).

Example 2

The same fibers as in Example 1 was dyed in a dye bath containing 5 ⁰ Ai of dye, based on fiber weight

COOH

(assumed structure where R is CH.j or CF; s and Ri is H or CHi) and with the aid of Formic acid was kept at a pH of 3.5 to 4.0. The remaining staining conditions were the same as in Example 1. The dye uptake obtained is shown in Table II below specified.

Table II Fibers
No. 1 2 3 4th Dye-
recording
i "1 0 85 89 92 95

The lightfastness had a grade value of 6 in all cases and the washfastness in all of them Cases a grade value of 5.

Example 3

50 parts by weight of aluminum powder was dispersed in 325 parts by weight of xylene, and the obtained Suspension was heated to reflux. 220 parts by weight of anhydrous were added to the suspension Ethanol, mixed with 0.25 parts by weight of mercury (II) chloride and a small amount of an iodide, dripped.

After all of the ethanol had been added, heating was continued. After the The suspension was nitrated with evolution of hydrogen. Under nitrogen and under reduced pressure the xylene was driven off, 200 g of aluminum triethylate being obtained. 162 parts by weight of aluminum triethylate and 284 parts by weight of stearic acid were dissolved in benzene and allowed to operate for about 2 hours Heating to the boiling temperature of the benzene brought to reaction. Then ethanol was added, to precipitate the product, after drying 354 parts by weight of monostearoyloxy diethoxy aluminum (hereinafter referred to as "substance B") were obtained.

The same crystalline polypropylene as in Example 1 was with this substance in the in Table III given proportions and mixed the mixture at a temperature of 220 C to tablets deformed. This was followed by a conventional melt, spinning process at a temperature of 250.degree subjected and stretched at a temperature of 130 C to 5 times the original length, to make fibers.

These fibers were rinsed in the same manner as in Example 1. After washing with water the fibers were dyed in a dye bath containing 3%, based on fiber weight, C.I. Stain blue I (C. 1.43 830), and 5%, based on the fiber weight, Contained 48% acetic acid. The liquid ratio was 1:50, and it was 90 minutes at one Colored temperature of 90 C. During dyeing, 4 "/ o based on fiber weight was 85% acetic acid admitted. Then the colored fibers became

taken out and soaped in the same manner as in Example 1.

All of the dyed fibers obtained were light blue in color. After 48 hours of irradiation no discoloration was observed with a fadeometer

determine or discoloration. The wash fastness was excellent and corresponded to a grade value of 5. Die other properties of the fibers obtained and the dye adsorption values are given in Table III.

Table III

No. composition
(Weight percent) Substance B Dry tensile strength Dry extensibility Dye uptake Polypropylene (Weight percent) (g / den) (";,> (%) 1 99 1 6.7 28.0 56 2 98 2 6.5 29.0 60 3 95 5 6.6 29.5 65 4th 90 10 5.8 32.4 85

Example 4

The same fibers as in Example 3 were dyed in a dyebath which was 5%, based on fiber weight, of the dye

O OH

RHN

(putative structure), where R is a lower alkyl radical and was adjusted to a pH of 4 to 5 with the aid of acetic acid. It was dyed by the same procedure as in Example 1.

The products obtained had a light purple hue. The dye uptake and the authenticity were excellent, as can be seen from Table IV.

Table IV

No. dye
recording
(° ol Authenticity to
sunlight
(Degree value) Washfastness
(Degree value) 1
2
3
4th 75
87
91
89 5
6th
more than 6
more than 6 5
5
4 to 5
4 to 5

Example 5

Following the same procedure as in Example 1, but using twice the amount Stearic acid, was the compound

(hereinafter referred to as "Substance D").

Crystalline polypropylene, which is an intrinsic

Had a viscosity of 1.6, was with the substance D mixed in the proportions given in Table V. The mixture became after fibers are produced using a conventional melt spinning process. These fibers were stained blue with the help of C.I. 27 (C.I. 67 415) dyed under the same conditions as in Example 1, whereby the fibers received a bluish purple color. The fiber properties and dyeability are given in Table V. specified.

Table V

No. Polypropylene
(Weight percent) Substance D
(Weight percent) Dry
tear resistance
(g / den) Dry
extensibility
(%) dye
recording
(%) Color fastness
opposite to
sunlight Washfastness 1
2
3
4th 99.5
99
98
96 0.5
1
2
4th 6.5
6.4
6.3
6.2 27.5
28.0
29.5
31.0 75
88
95
97 6th
6th
more than 6
more than 6 5
■ 5
5
5

909507/1533

ίο

Example 6

The substances listed in Table VI were mixed with crystalline polypropylene in an amount of 2 percent by weight mixed homogeneously. These mixtures were made using the same procedure as in example 1 fibers produced. The fibers obtained were dyed as in Example 2. The results are summarized in Table VI.

Table VI

Additives Dry Dry dye No. tear resistance extensibility recording (CnHsöCOOfcAlOCoHä (g / den) (%) (%) 1 (Ci ₇ H ₃₅ COO) OAIOC ₁ H.) 6.5 29.5 95 2 (Ci ₇ H ₃₅ COO) IAI (OC ₂ Ho) ₂ 6.5 29.8 94 3 (Ci ₇ H ₃₅ COO) OAIOH 6.2 25.8 90 4th (Ci ₇ H ₃₅ COO) IAl (OH) ₂ 6.0 30.1 77 5 . 5.87 32.0 85

Experiments 4 and 5 represent comparative experiments.

The fastness of the products obtained to sunlight was in all cases higher than 5 degrees, and the wash fastness was excellent, corresponding to a value of 5.

When cross sections of these colored products were viewed under an optical microscope, a uniform coloration could be determined in experiments nos. 1 and 2. No. 3 was also evenly, but scattered some deeper colored spots. No. 4 showed the same dye distribution. No. 5 had numerous stains, with almost all of the dye being concentrated on these stains was. The results in the table show that the additives according to the invention are tolerated is excellent.

Example 7

The same fibers as in Example 5 were 5%, based on fiber weight,

OH

30th

35

a dye of the putative structure in which R is H or lower alkyl, according to the process colored by example 4.

The hue of the colored products obtained was light orange. Cross sections of the colored fibers showed uniform coloration, and dye uptake and fastness were excellent, such as can be seen from Table VII.

Table VII

No. Dye uptake
( ⁰ O) authenticity
opposite to
sunlight Washfastness
(Degree value) 1
2
3
4th 77
86
92
93 5 to 6
5 to 6
6th
6th 5
5
5
4 to 5

Claims (4)

Patent claims: 1. Polypropylene fibers with improved colorability, which contain aluminum soaps, characterized by being polypropylene and 0.1 to 10 percent by weight of at least one compound of the general formula (RiCOOUAl (ORo) _n contain, in which Ri is an alkyl radical having 7 to 29 carbon atoms, R _{2 is} an alkyl radical having 1 to 18 carbon atoms and m and η are 1 or 2, where m + η = 3. 2. Polypropylene fibers according to claim 1, characterized in that they are polypropylene as well 0.1 to 10 percent by weight of at least one compound of the general formula (RiCOO) _7n Al (ORo) ,, where Ri is an alkyl radical having 7 to 17 carbon atoms and R _{2 is} an alkyl radical having 2 to 12 carbon atoms and m and η are 1 or 2, where m + η = 3. 3. Polypropylene fibers according to claim 1 and 2, characterized in that they are 1 to 5 percent by weight at least one compound of the general formula (RiCOO) _m Al (OR ₂ ) " contain. 4. Polypropylene fibers according to claim 1 to 3, characterized in that the aluminum soap is one of the general formula (RiCOO) _m Al (OR.) " contain, in which Ri and Ro have the meanings given and m = 2 and η = 1.