DE1278691B - Process for the production of polypropylene fibers with improved dyeability - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

DOIf

German class: 29 b-3/65

Number: 1278 691

File number: P 12 78 691.3-43 (M 63614)

Filing date: December 23, 1964

Opening day: September 26, 1968

The coloring of fibers or threads made of polypropylene is because of its hydrophobic properties difficult, and the conventional dyes do not penetrate deeply. In addition, polypropylene does not have any sufficiently strong "active centers" to bind dyes tightly. Even dyes that get into the interior The fibers or threads can penetrate easily during washing or dry cleaning discolored.

There are already various methods of dyeing difficult-to-dye polypropylene fibers or threads known. In so-called pigment coloring, the fiber-forming material is removed from the spinning process colored pigments incorporated (cf. the magazine "Modern Plastics", 37, No. 3, p. 119, as well as the German Patent Specification 1,073,681). According to this method, colored molded articles can be widened Preserved range of relatively true colors. The cleaning of the devices when changing However, the pigment used for coloring is expensive. Besides, it's not easy to be a big one Assortment of paints for making commercial products.

In British Patent 932,897 and U.S. Patent 2,984,634 there are methods of making of dyeable polypropylene fibers, the polypropylene being aluminum stearate or metal salts of Ni, Cr, Co, Al, Ti or Zr of aliphatic carboxylic acids with 6 to ^ carbon atoms or incorporated into oleic acid. These processes can be used to produce fibers that are superior Have fiber properties and good dyeability for dyes which have coordinative bonds Metal atoms can enter. However, the fibers made by these methods only have one poor resistance to light. Accordingly, these fibers easily lose their superior mechanical properties Properties and therefore become worthless.

It is also known, for. From the Italian patent 470 458 and the USA patent 2 940 949, to incorporate a high molecular weight compound into the polypropylene before the addition of color and then to spin the mixture or according to z. B. the Italian patent 548 249 and the Belgian Patent 590 556 to subject polypropylene fibers to a chemical treatment in order to have them to provide active centers. In the former method you have to use the polypropylene with a Mix high molecular compound, which is also sufficiently compatible with this. To achieve For darker colors, the high molecular compound must be added in a relatively large amount.

Process for the production of
Polypropylene fibers, with improved
Dyeability

Applicant:

Mitsubishi Rayon Co., Ltd., Tokyo

Representative:

Dr. rer. nat. V. Vossius, patent attorney,
8000 Munich 23, Siegesstr. 26th

Named as inventor:

Tsuzuku Yamamoto,

Akira Ichikawa, Ohtake-shi;

Masakazu Honda, Mitaka-shi;

Minoru Sasaki,

Kazuo Senda,

Eiji Nakajima,

Shigenobu Masunaka, Ohtake-shi;

Masahiro Hirose, Hiroshima-ken (Japan)

Claimed priority:
Japan December 28, 1963 (71 055),
dated December 30, 1963 (71 604)

Therefore, it is difficult to obtain fibers which have good dyeability and at the same time the abrasion resistance, Maintain fatigue resistance and strength that polypropylene possesses. The chemical Treatment requires uniform treatment and sufficient separation of the treatment agent. However, this is not technically easy to do carry out. Furthermore, according to the known methods for improving the dyeability, colors

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a wide range of colors, which ranges from dark to light colors and has superior authenticity, hardly can be obtained.

The invention relates to the production of polypropylene fibers with improved dyeability in a wide range from dark to light colors, achieving true colors.

The inventive method for producing polypropylene fibers with improved dyeability by spinning a mixture of polypropylene with = a metal salt of stearic acid characterized in that the spinning mass is a mixture of polypropylene and 0.1 to 10 percent by weight, based on the polypropylene, a mixture of the aluminum or zinc salt of Stearic acid and the nickel salt of stearic acid in a ratio of 50:50 to 90:10. These Polypropylene fibers or jades are dyed with dyes that contain the aforementioned metal atoms, which are contained in the fibers or threads, form chelate compounds.

According to the invention, excellent dyeable polypropylene fibers or threads can be obtained by the synergistic effect of two different metal salts of stearic acid, whereby the dye utilization is considerably better than using just one of these salts. The colorations obtained are also brilliant in the entire color range from dark to light. Since the coloring range is wide, the The variety of colors obtained is practically unlimited. The colored fibers or threads are real, in particular against sunlight and also against washing, dry cleaning and abrasion.

Polypropylene fibers made by spinning a mixture of polypropylene and the nickel salt are obtained from stearic acid alone, have a good depth of color and lightfastness in the dyed state, but the brilliance is not good, there is a possibility of variation of the colors in the light color range bad, as well as the whiteness of the uncolored structures. Polypropylene fibers made by spinning a mixture obtained from polypropylene with the zinc salt of stearic acid have a better one Whites, when colored, the depth of color and brilliance are comparatively good, but the colored ones have Forms an extremely poor lightfastness. Polypropylene fibers made by spinning a mixture obtained from polypropylene with the aluminum salt of stearic acid have in uncolored Condition is good whiteness, and the colored structures have good brilliance, but the depth of color is of the colored structures unsatisfactory, and the possibility of varying the colors in the dark color range is bad.

Thus, polypropylene fibers or filaments are made by spinning a mixture of polypropylene with an aluminum salt of stearic acid alone can be obtained with regard to the brilliance of the colored ones Structures, the authenticity of the colors, the possibility of varying the colors and the like are of little use.

The polypropylene fibers produced according to the invention, on the other hand, retain the color brilliance and at the same time show a synergistic effect in terms of lightfastness. Also with these modified polypropylene fibers the possibility of varying the colors in the range from dark to light colors practically unlimited. If the polypropylene fibers are those desired according to the invention Should have properties, they cannot always be achieved by simply mixing any amounts the zinc salt or aluminum salt and the nickel salt of stearic acid, but the metal salt mixture used according to the invention should mainly consist of the zinc salt or aluminum salt of stearic acid and relatively small amounts of the nickel salt of stearic acid exist.

In the case of a mixture of the zinc or aluminum salt of stearic acid, the one proportionately give low lightfastness, and the nickel salt of stearic acid, which has a relatively high Imparts light fastness, it was to be expected that the light fastness with increasing content of nickel salt and a constant total amount of the metal salt mixture is increased. One can also expect that the whiteness of the uncolored structures and the brilliance of the colored structures increase with increasing Content of nickel salt and constant amount of the metal salt mixture decreases. The white and the The brilliance is deteriorated as the content of nickel salt in the metal salt mixture increases. Surprisingly, however, the lightfastness decreases with an increasing content of nickel salt in the metal salt mixture not unlimited, but a potentiated synergism can be observed, d. i.e., using a relatively small amount of the nickel salt of stearic acid in the metal salt mixture the lightfastness is improved to the same extent as when a large one is used Amount of the nickel salt of stearic acid alone. After adding a certain amount of the nickel salt of the stearic acid to polypropylene, the lightfastness no longer increases in spite of further addition.

On the other hand, the whiteness of the uncolored structures and the brilliance of the colored structures are all the better is, the lower their nickel salt content, the addition of more nickel salt than necessary is unfavorable and even harmful.

Presumably the addition of a small amount of the nickel salt of stearic acid causes the zinc or Aluminum salt of stearic acid changes the coagulation state of the chelate dye in the Fibers that are approaching the coagulation state created by the nickel salt of stearic acid is caused by itself, d. that is, the state shifts to a monomolecular dispersion that of a multimolecular coagulated dispersion. It has been found that the addition of nickel salt of stearic acid not only extremely prolongs the time required for discoloration, but also the Order of reaction of the discoloration of the colored structures as a function of the dye concentration changes from the second order to the zero order, i.e. makes it independent of the concentration.

Presumably, nickel atoms can also cause the light-excited unstable state of the dye molecules move to the stable state in colored structures or shield ultraviolet rays. Another important effect of this combination is the increase in the possibility of variation the colors produced by dyeing the polypropylene fibers and / or the lightness of the Creation of dark colors.

In general, the zinc salt of stearic acid is the nickel salt in terms of colorability Underlay fibers. For example, this gives zinc salt

the stearic acid does not have such good dyeability for acetylacetonate dyes as the nickel salt. Farther results in the aluminum salt of stearic acid except with anthraquinone, ο, ο'-dihydroxyazo-, 8-hydroxyquinoline- and salicylic acid dyes hardly any dyeability. In contrast, the nickel salt enables one good dyeability with numerous dyes, e.g. B. o-Hydroxy-azobenzothiazole and acetylacetonate dyes and the aforementioned dyes.

Accordingly, one should expect the color range to be increased and the dark colors to be lighter can be obtained by combining the nickel salt of stearic acid with the zinc salt of Stearic acid.

Metal salts of stearic acid which can be used according to the invention are aluminum monostearate, aluminum distearate, Aluminum tristearate, nickel monostearate, nickel distearate, zinc monostearate and zinc distearate. These compounds can be used not only individually but also in a mixture. For example suitable There is also a mixture of aluminum monostearate and aluminum distearate. Furthermore, these Compounds readily prepared by known methods or are commercially available.

The metal salts of stearic acid are used in an amount of 0.1 to 10 percent by weight, preferably from 0.5 to 5 percent by weight, incorporated into the polypropylene. The mixing ratio of The nickel salt of stearic acid to the zinc or aluminum salt of stearic acid is in the range of 50:50 up to 90:10, preferably -ΰΟ: 40 to 85:15. That The nickel salt of stearic acid is added to the polypropylene in an amount of at least 0.05 percent by weight incorporated.

If the total amount of the metal salt mixture is less than 0.1% by weight, none can be obtained obtained satisfactory results. The use of more than 10 percent by weight is not favorable, since the spinnability and the properties of the threads or fibers obtained are impaired.

The aforementioned metal salts of stearic acid are mixed with polypropylene in the proportions mentioned mixed according to methods known per se. In general, a mixture of the metal salts is mixed with polypropylene powder, the The resulting mixture is shaped into cookies, and the resulting cookies are spun in the melt. Before making the cookies, dispersants, stabilizers and matting agents, such as titanium dioxide, may be added.

The dyes usable for dyeing depend on the kind of metal salts of stearic acid and their combination. Dyes, the chelate compound with the metal atoms of the invention Forming stearates used belong to the group of anthraquinone, ο, ο'-dihydroxyazo-, arylazo-8-hydroxyquinoline, o-hydroxyazothiazole and o-hydroxyazopyrazolone dyes. In addition, azo, Azomethine, ο, ο'-dihydroxyazomethine, o-hydroxyketone, ο - hydroxy - ο '- carboxyazo-, formazan, Salicylaldoxime and hydroxynaphthoquinone dyes can be used.

It can also disperse dyes, oil- and fat-soluble dyes and mordant dyes, the metal 1-chelate can be used.

The invention is further illustrated by the following examples. Percentages relate to based on weight, unless otherwise stated.

example 1

Zinc distearate (I) and nickel distearate (II) in a total amount of 2% are incorporated into polypropylene with an intrinsic viscosity of 1.4 (determined in tetralin at 135 ^° C.) in the proportions given in Table I below. In addition, 0.9% of a stabilizer is added. After thorough mixing, the mass is molded into cookies to be spun at 24O ⁰ C in the melt. The filaments are stretched at 120 ⁰ C to the 5,6fache their original length and annealed at 130 ⁰ C. The threads obtained in experiments 2 to 6 have a strength of 5.3, 5.2, 5.2, 5.2 and 5.2 g / den and an elongation of 40, 40, 38, 40 and 39%. The threads obtained are washed in a bath which contains 0.5 g / l of a polyoxyethylene alkyl ether RO (C ₂ H ₄ O) _n H, η = 42, and 0.1 g / l of sodium pyrophosphate. The liquor ratio is 50: 1, the temperature 70 ° C. and the duration of the treatment 15 minutes. After that, the threads are washed thoroughly with water.

The threads are dyed under the following conditions: Either a dye is used as the dye the formula

R = alkyl

used in a concentration of 5% of the thread weight. The dispersant used is 5% of the thread weight of an anionic wetting agent for (A) or 5% of the thread weight of a nonionic wetting agent for (B). The pH is adjusted to 3.5 to 4.0, the liquor ratio is 50: 1, and the temperature is gradually increased so that the boiling point, starting from 50 ^° C., is reached after 30 minutes. The material is often stirred to ensure that it is evenly colored. After 90 minutes of boiling, the threads are removed from the dye bath and soaped in a bath containing 0.5 g / l of the polyoxyethylene alkyl ether and 0.5 g / l of sodium carbonate. The liquor ratio is 50: 1, the soaping 90 ⁰ C and the treatment time 20 minutes. The dyed material is then washed thoroughly with water and dried.

For comparison, the compounds (I) and (II) polypropylene are incorporated individually in an amount of 2%, and the threads obtained are washed, dyed and soaped. The results are in Table I. compiled.

Table I.

attempt Metal salt,% I. II dye Utilization hue brilliance Lightfastness No. 2 0 A. Degree Purpurstichigrot 5 3 1 1.8 0.2 A. 70 Purpurstichigrot 5 4 to 5 2 1.6 0.4 A. 74 Reddish purple 4 to 5 5 3 1.4 0.6 A. 78 Reddish purple 4th 5 to 6 4th 1 1 A. 78 Reddish purple 3 to 4 6th 5 0.4 1.6 A. 82 Reddish purple 3 6th 6th 0 2 A. 80 Reddish purple 3 6th 7th 2 0 B. 75 Red 5 4th 8th . 1.8 0.2 B. 75 Reddish brown 5 5 to 6 9 1.6 0.4 B. 80 Brown 4 to 5 6th 10 1.4 0.6 B. 79 Brown 4th 6th 11 1 1 B. 81 Brown 3 6th 12th 0.4 1.6 B. 80 Brown 3 6th 13th 0 2 B. 77 Brown 3 6th 14th 76

and 1.5% incorporated and mixed thoroughly. The mass is spun and drawn according to Example 1. The strength of the threads is 5.4, 5.2 or 5.1 g / denier and the elongation is 41, 41 or 39%. The threads obtained are washed, dyed and soaped according to Example 1, and is used as a dye either a dye of the formula

CF ₃

In this table, tests No. 1, 7, 8 and 14 are comparative tests. The degree of utilization is a measure of the dyeability of polypropylene. The concentration of the remaining dye solution is determined colorimetrically. For brilliance, the value 5 means the best value and the value 1 the worst value. The lightfastness is determined using the blue scale using the fade-o-meter method Test standard JIS-L-1044 (1959) determined.

From Table I it can be seen that using the combination of zinc distearate and nickel distearate the dye utilization is considerably increased compared to the use of the individual stearates. Furthermore, with a high content of zinc distearate, the light fastness is considerably improved, but the Brilliance not affected.

or a dye of the anthracene series (similar to the 4-nitro example 2 alizarin) (D) is used.

For comparison, the compounds (III) and

Aluminum distearate (III) and nickel stearate (II) 45 (II) individually in an amount of 2% polypropylene are incorporated in a total of 2%. The threads obtained are washed, Example 1 used polypropylene powder in the men- dyed and soaped, and the results obtained The ratio of 1.5 and 0.5%, 1 and 1% and 0.5 are listed in Table II.

Table II

attempt Metal salt, ° ₀ II III dye Utilization hue brilliance Lightfastness No. 2 0 Degree 1.5 0.5 C. 0
0 yellow 5 4 to 5 15th 1 1 C. 48 Orange yellow 5 6th 16 0.5 1.5 C. 59 Orange yellow 5 > 6 17th 0 2 C. 76 Orange yellow 4 to 5 > 6 18th 2 0 C. 75 Orange yellow 4th > 6 19th 1.5 - 0.5 D. 70 Purpurstichigrot 5 5 20th 1 1 D. 57 Reddish purple 5 6th 21 0.5 1.5 D. 65 Reddish purple 5 6th 22nd 0 2 D. 64 Reddish purple 4th 6th 23 D. 66 Reddish purple 3 to 4 6th 24 58

In this table, tests No. 15, 19, 20 and 24 are comparative tests.

From Table II it can be seen that using the combination of aluminum distearate and nickel distearate the degree of utilization of the dye and the lightfastness of the colored products are considerable improved, but the brilliance is not impaired.

Example 3

Polypropylene threads which contain 1% aluminum distearate (III) and 1% nickel distearate (II) and which according to Example 2 are prepared using a dye of the formula

; 0- K k OH 10 COCH ₃ C ₂ H ₅ the formula N = N- -CH respectively. COCH ₃
COOH

= N-

OH (G)

OH

C ₂ H ₅ O

CH ₃

or the formula

(R = H or CH ₃ )

colored according to example 1. The threads are washed, then dyed and then soaped. To the (E) Compounds (III) and (II) are compared

Polypropylene incorporated individually, and the threads obtained in each case are washed in the same way, colored and then soaped. The results are shown in Table III.

Metal salt,% III ... Ii ■ Tabel III hue Lightfastness attempt 2 O dye Utilization No. 1 1 Degree, % 1 25th O 2 E. 8th green 6th 26th 2 O E. 68 green 6th 27 1 1 E. 79 - 1 28 O 2 F. 10 Red 6th 29 2 O F. 90 Red 6th 30th 1 1 F. 94 orange 4th 31 O 2 G 80 orange 6th 32 G 71 - 1 33 G 15th

In Table III the tests 25, 27, 28, 30, 31 ₄₀ B is ρ ie 1 4 are

and 33 comparative tests. The procedure according to Example 1 is repeated,

From the table it can be seen that when used, however, either 2- (l'-naphtholder Metal salt combination the dyeability is improved, while using the individual metal salts

good dyeability cannot be obtained.

'-ylazo) -6-ethoxybenzthiazole (H) or 1- (2'-hydroxy-5'-methylphenylazo) -2-naphthol (J) used.

The results are shown in Table IV.

Table IV

attempt Metal salt,% I. II dye Utilization hue brilliance Lightfastness No. . 2 0 Degree, % 34 1.8 0.2 H 70 blue 5 4th 35 1.6 0.4 H 77 blue 5 5 to 6 36 1.4 0.6 H 78 blue 4 to 5 6th 37 1 1 H 80 blue 4 to 5 6th 38 0.4 1.6 H 80 blue 4th > 6 39 0 2 H 79 blue 3 to 4 > 6 40 2 0 H 77 blue 3 to 4 > 6 41 1.8 0.2 J 45 Red 5 3 42 1.6 0.4 J 58 Red 5 5 43 1.4 '0.6 J 65 Red 4 to 5 6th 44 1 1 J 67 Red 4th 6th 45 0.4 1.6 J 63 Reddish brown 3 to 4 6th 46 0 2 J 61 Reddish brown 3 6th 47 J 60 Brown 3 6th

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In Table IV, Runs Nos. 34, 40, 41 and 47 are comparative runs.

From Table IV it can be seen that when a small amount of nickel distearate is used, combined zinc distearate considerably improves the lightfastness of the dyed threads and not the brilliance is impaired.

Example 5

The process according to Example 2 is repeated, but the dye is 5- (4'-dodecylphenylazo) -8-hydroxyquinoline (K) used. The results are shown in Table V.

Table V

attempt Metal salt,% IH II dye Utilization hue brilliance Lightfastness No. 2 0 Degree, % 48 1.5 0.5 K 57 Orange yellow 5 5 49 1 • ι K 85 Orange yellow 5 > 6 50 0.5 1.5 K 93 Orange yellow 4 to 5 > 6 51 0 2 K 90 Orange yellow 4th > 6 52 K 89 Orange yellow 4th > 6

In Table V, Runs Nos. 48 and 52 are comparative runs.

From Table V it can be seen that when the metal salt combination is used, the dye utilization rate considerably improved and the lightfastness of the dyed threads is also improved.

Claims (2)

Patent claims: 1. Process for the production of polypropylene fibers with improved dyeability by spinning a mixture of polypropylene with a metal salt of stearic acid, thereby characterized in that the spinning mass is a mixture of polypropylene and 0.1 to 10 percent by weight, based on the polypropylene, a mixture of the zinc or aluminum salt of stearic acid and the nickel salt of Stearic acid used in a ratio of 50:50 to 90:10. 2. The method according to claim 1, characterized in that there is a mixture of stearic acids Metal salts used in which the ratio of the zinc or aluminum salt of stearic acid to the nickel salt of stearic acid is 60:40 to 85:15. 809 German / 547 9. U β Bundddruckerei Berlin