DE2420151A1 - ARTIFICIAL FIBERS AND THE METHOD OF MANUFACTURING THEM - Google Patents

Description

Synthetic fibers and methods of their manufacture

The invention relates to new synthetic fibers with a good surface smoothness and a good grip (feel) and a method for their manufacture.

Recently, organopolysiloxanes have been used as finishing agents armor) have been developed for various types of fiber in order to reduce their frictional resistance and make them heat-resistant and to make it water repellent. Although some of these polysiloxanes appear on the surface of a fiber product by themselves cure, none of these polysiloxanes result in a coating film with a sufficiently low frictional resistance as well a good grip (a good feel) and a sufficient resistance to organic solvents. Also is hitherto no suitable method for applying these organo- 'polysiloxanes to fibers is known. Examples of curable organic Polysiloxanes that are usually used for the purpose given above are Hethylhydrogenpolysiloxan (the formulas A and B given below), methylvinylpolysiloxane (formula C given below), epoxy groups polysiloxanes containing (the following formula D), amino group-containing polysiloxanes (the following given formula Ξ), polysilicon containing oxyalkylene groups

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oxane (the formula F given below) and the like. In addition, polysiloxanes are available in which the methyl groups of the compound F are partially replaced by hydrogen atoms or hydroxyl groups.

H \ CH ₂ SiOl- Si-GH _x CH, / ¹¹ CH-,

A, a mixture of

CH, -

CH, ι ο

SiO

CB,

- OH and A or B

CH,

Mixture of C and A or B.

CH,
SiO

CH, - SiO -

CH

SiO J - Si - CH,

iCH, / ^m \ R-CH-CH ^ CH, \ / ^d * 0

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CH,

E CH_ - SiO -I SiO 1-4 SiOh-- Si - CH,

CH, \ CH, / ^m \ E-HE ¹ ₂ CH,

? ^H 3 CH ₃ - SiO -I SiO L ~ I SiO L- Si - CH,

CH,

When using these finishing agents (surface treatment agents) So far, however, no materials have been used for use as filling, artificial leather, carpet materials and the like. Obtain satisfactory properties, as shown by the examples below.

On the other hand, in the ^ Japanese Patent Publications _r lf _# 44-21591 / 1969 and 44-26436 / 1969, although methods for treating synthetic fibers (synthetic fibers) with acrylic resin and methylhydrogenpolysiloxane for the production of good filling materials (cushion materials) with an improved compression deformation recovery properties described in this In some cases, however, the decrease in frictional resistance of these products is not sufficient for the intended use. In addition, the viscosities of polysiloxanes commonly used as agents for treating fiber materials are at most about 100,000 cSt at 25 ° C, and polysiloxanes with higher viscosity values have not been used for treating fiber materials as filling material and the like. It is believed that this is because the difficulty in treating the fibers with such polysiloxanes is so great

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are larger, the higher the viscosity of the polysiloxane is, an uneven distribution of the polysiloxane on the fibers occurs and the friction resistance of the highly viscous polysiloxanes is evidently higher than that of low viscosity polysiloxanes and also the cost of the first-mentioned polysiloxanes are considerably higher than for the last-mentioned polysiloxanes. After extensive Investigating these problems, it has now been found that a silicone film coating can be applied to fibers can, which is characterized in that the silicone as structural elements carbon, hydrogen, nitrogen and oxygen, the content of nitrogen and the total content of the structural elements being determined by Elemental analysis, in each case within the range from 1 to 5 or 4-0 to 60% by weight, based on the silicone, is and the silicone always has four characteristic absorption bands at a wavelength in the vicinity of 800, 1000 to 1100, 1260 and 34-50 cm, measured by infrared spectroscopy, and which has improved surface properties. In particular, it has been found that the film coating from a silicone on the fibers, which from a combination of an aminoalkoxysilane and an organopolysiloxane with produced with the aminoalkoxysilane condensable hydroxyl groups Has been made the same structure as given above and has synthetic fibers in the form of fibers for example used as filling material, advantageous properties, such as low frictional resistance, better surface smoothness and high compression deformation recovery.

Namely, it has been found that when a reactive polysiloxane is combined with an aminoalkoxysilane is used, the resulting polysiloxane with a high viscosity, which has not previously been used for coating

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has been, contrary to the conventional view, one for the intended use according to the invention has excellent effect. These reactive polysiloxanes which are suitable according to the invention are those that have a viscosity greater than 2 ^ 0,000 cSt and have at least two hydroxyl groups in their molecule and have the following general formula

^R n ^Si Vn (D

wherein R is a lower alkyl group and η is 1.8 to 2.1; Examples of such compounds are Dimethylpolysiloxane with terminal hydroxyl groups in the molecule.

On the other hand, aminoalkoxysilanes with a primary and / or secondary amino group in the are used as crosslinking agents Molecule are used which have the following general formula

^{23 4} ) ₃ _ _m (2)

wherein R is a hydrogen atom, a lower alkyl group or an aminoalkyl group, R ^ a hydrogen atom or a

'4

Lower alkyl group, R a lower alkyl group, 1 a positive integer and m the number 0 or 1; Typical examples of such compounds are γ -aminopropyl-triethoxysilane, γ - (ß-aminoethyl) aminopropylmethyldimethoxysilane, V- (ß-aminoethyl) aminopropyltrimethoxysilane.

The present invention, which is described in more detail below, relates to the production of synthetic fibers (syn-

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theses fibers) with a latent crimpability, "in which an emulsion of the polysiloxane (i) and the aminoalkoxysilane (2), emulsified in a suitable emulsifier, with the simultaneous presence of a hardener, is applied to the surface of the fiber after stretching and then the The fiber obtained in this way is ^{heated to a temperature between 120 and 200 °} C. in order to generate crimps and in order to cure the polysiloxane on the surface of each individual filament (thread)

Compression set recovered better and has a better grip (feels better) by applying a Film coating with a low frictional resistance. In addition, the film layer produced in this way is made of the Silicone is characterized by the fact that the silicone consists of the structural elements carbon, hydrogen, nitrogen and Oxygen consists, the content of nitrogen and the total content of the structural elements, determined by elemental analysis, in each case within the range from 1 to 5 or from 40 to 60% by weight, based on the silicone, and the silicone always has four characteristic absorption bands at a wavelength in the vicinity of 800, 1000 to 1100, 1260 and 3 450 cm, measured by infrared spectroscopy, having. The fiber obtained in this way is suitable as a filling material (cushioning material), for example as wadding for an artificial feather quilt or an artificial feather pillow, as well as a base fabric for artificial feathers or for a carpet, without being after the treatment with the organopolysiloxane must be subjected to further treatment, and it also has better resistance to washing and dry cleaning on.

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As a lower alkyl group is suitable for the best S and Zl

E of the organopolysiloxane of the general given above Formulas (1) and (2) used in the invention preferably the methyl group. The viscosity of the polysiloxane of the general formula (1) should be more than 250,000, preferably more than 500,000 and in particular more than 5,000,000 cSt. Namely, an organopolysiloxane having a low viscosity has been found to be insufficient Surface smoothness and poor durability, while on the other hand a polysiloxane with a too high viscosity difficult in the process according to the invention is to be emulsified. The polysiloxane (1) alone is able to make synthetic fibers smooth by adding the aminoalkoxysilane (2) in an amount of 1 to 30, preferably in in an amount of 5 to 15% by weight to the polysiloxane (1) the surface properties of the treated fiber for their Use as wadding material and the like. Improved even further, so that, for example, properties such as the. ". Surface smoothness and the durability of the obtained fibers can be improved to an even greater extent.

Salts of aliphatic acids with metal ions with two to four valences, such as magnesium acetate, Zinc acetate, cobalt isooctylate, lead isooctylate, tetrabutyl titanate, zirconium acetate and dibutyltin diacetate, be used.

In one embodiment of the invention, it is important to use the polysiloxane (1) and the aminoalkoxysilane (2) in the emulsified state. The reason for this is that since the viscosity of the polysiloxane itself is very high, it must be lowered for ease of handling, and the apparent viscosity of the emulsion may be so low that it can be easily handled. The preferred concentrations of the emulsion are 0.1 to 20 % by weight of poly

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siloxane (1) or 0.001 to 6% by weight of aminoalkoxysilane (2), where the sum of these two components in the emulsion is 0.101 to 26, preferably 0.5 to 10% by weight amounts to.

Usual nonionic surface-active agents can be used as emulsifying agents Agents such as polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers and polyoxyethylene esters of aliphatic Acids and the like, common anionic surfactants such as polyoxyethylene alkyl allyl ether sodium sulfate, and common cationic surfactants such as alkyltrimethylammonium chloride, be used.

The emulsion of the polysiloxane and the aminoalkoxysilane can be applied to the fiber all at once or separately and the amount of silicone applied in the form of an emulsion is 0.01 to 2, preferably 0.1 to 0.7% by weight, based on the fiber weight. The amount is quite small compared to the amount adhered to the fiber in the conventional processes. In addition, the emulsion can be applied to the fibers by a further method in which they are dipped into the emulsion, the emulsion is sprayed onto the fibers, sprayed on and the like. The fibers are treated with the emulsion by a suitable method, the method depending on according to the present fiber form is selected from the processes given above. When treating the fibers in the form of a yarn with the emulsion after drawing and subsequent heat treatment, for example, the emulsion is preferably applied to the yarn after crimping by spraying.

The emulsion of a polysiloxane used in the invention with such a high viscosity can be polymerized by

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of a low molecular weight organosiloxane in emulsion can be prepared in a conventional manner.

Together with the emulsion used according to the invention can also use finishing agents (surface treatment agents), as commonly used in the fiber industry are used in an amount of less than 0.2, preferably less than 0.1 wt .-%. As long as that effect according to the invention is not impaired, dimethylpolysiloxane with a low viscosity, previously used and therefore known, and other reactive polysiloxanes such as those described above are specified, can be used together with the polysiloxane (1) in an allowable amount. Preferably are in particular Polysiloxanes with polyoxyalkylene groups in their molecules in a small amount, i.e. in such an amount, which is below 50% by weight, together with the polysiloxane (1) used when the antistatic properties of the treated fibers increase.

The synthetic fibers produced by the process according to the invention, the surface of which is coated with a silicone, are characterized in that the silicone has carbon, hydrogen, nitrogen and oxygen as structural elements, the nitrogen content and the total content of the structural elements being determined by elemental analysis , in each case within the range from 1 to 5i, preferably from 1 to 3 or from 40 to 60, preferably from 45 to 55% by weight, based on the silicone, and they are characterized in that the silicone always has four characteristic absorption bands at a wavelength in the vicinity of 800, 1000 to 1100, 1260 and 3450 cm " ¹ , measured by infrared spectroscopy. When the total content of structural elements, determined by elemental analysis, is below 40 wt

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Smoothness and durability (service life) and they only have the same surface appearance or the same feel (the same feel) as those made by a conventional process without having the desired lubricity % By weight, the fibers obtained have an undesirable property that they turn yellow during the heat treatment. In addition, when the total structural element content appears to be within the range of 40 to 60% by weight by replacing the aminoalkoxysilane with a considerable amount of other organic compounds, the resulting fiber does not have the superior surface appearance or feel * Also if the nitrogen content, determined by elemental analysis, is below 1 % by weight , the fibers obtained do not have the desired smoothness. On the other hand, if the nitrogen content is above 5% by weight, the obtained fibers are inferior in heat resistance.

Another characteristic feature of the present invention can be seen in the method of treating the fiber to be used. That is, the fiber to be used in the present invention may be a conventional fiber, and it should preferably be such a fiber which can be curled by heat treatment. ! fold coating the surface of the drawn fiber with an emulsion of the polysiloxane and the alkoxysilane in the simultaneous presence of a hardener occur present in the fiber latent crimps by a 2- to 20-minute ISärmebehandlung at 120 to 200, preferably at 140 to 180 ⁰ C in appearance, at the same time as the formation of a solid film coating layer on the surface of the fiber

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occurs. In this way, the fiber according to the invention can be easily manufactured.

An example of a synthetic fiber with a latent curl— availability is a filament with an axially asymmetrical Orientation achieved by quenching a spinning filament in a non-symmetrical manner immediately below the spinneret Melt spinning process has been produced, and a bicomponent filament, Consists of two components with different properties in terms of heat shrinkage. The former is easier to manufacture and is sufficient for the purposes of the present invention. As a synthetic fiber with a latent crimpability caused by asymmetrical quenching has been produced, fibers with a non-circular cross-section as well as those with a circular cross-section are available Disposal. For the purposes of the present invention, preferably those with a non-circular cross-section are used, because most of them have better compression deformation recovery (compression deformation recovery). Since the fibers obtained by treatment according to the invention with the organopolysiloxane have the characteristic Have properties that they have a low frictional resistance and consequently they are difficult to mechanically to crimp, it is expedient and advisable, according to the invention, as starting material such fibers with non-circular Cross-section rather than using circular cross-section which has latent crimpability and accordingly do not need to be mechanically curled again.

An example of a synthetic fiber with one of a circular Cross-section different non-circular cross-section and a latent crimpability, which are used as the starting material used in the method according to the invention

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can be, is one whose cross-section consists of a circular cross-section as a base body and some projections consists, the degree of orientation of the fiber from the projections to the base in the Way continuously changes so that the orientation at the projections is highest · The total area of the projections in the cross section is smaller than that of the circular part of the cross section as the main body. If the Cross-section is divided into two parts, namely in the inside of an inscribed circle along the circumference of the main body and the outside of the same, i.e. in two parts, each to the main body and belong to the protrusions, the ratio of the areas is A / B (A is the area of the first named part and B is that of the last-mentioned part) preferably at least 9 to at most 50. When the protrusions are also divided into a standard protrusion and the adjacent protrusion, the central angle is cc, formed by the standard projection and the adjacent projection with respect to the center of the base body is, preferably at least 4-5 to at most 135 °. Of course, other cross-sectional shapes, for example triangular, rectangular, star-shaped or hollow cross-sections can be used. In addition, a synthetic fiber can also be used can be used without latent crimpability, but in this case it is convenient to use the drawn one first To mechanically crimp yarn and then according to the invention with it To treat polysiloxane (1) and alkoxysilane (2) in combination with a hardener and then after sufficient Loosening (relaxing) each filament to harden. For loosening, a common method can be used, for example a mechanical opening or a method using a fluid can be used.

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The inventive method can be applied to synthetic fibers, such as for example, those made of a polyamide, polyolefin and polyvinyl chloride, which are melt-spun by melt spinning, can be employed preferably used on polyester fibers made from dibasic acids such as terephthalic acid and difunctional alcohols such as ethylene glycol such as polyethylene terephthalate or a copolymer thereof containing a third component, or polyether ester. In addition, the inventive Process also on such synthetic fibers or regenerated fibers, such as polyacrylonitrile, polyvinyl alcohol, rayon and acetate fibers, which are produced by wet spinning or dry spinning, can be used, and it can also be used on natural fibers, such as animal hair, z * .B. Wool and the like, Cotton and linen.

The fibers obtained by the process according to the invention can be used as filling material in pillows, quilts, piqué and as a base fabric for artificial feathers or carpets as well as for others Fiber materials or the like used for general purposes.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto. The parts specified therein are by weight and the intrinsic viscosity (intrinsic viscosity) C ^] of Polyäthylenteraphthalat was dissolved in a solution of a phenol / tetrachloroethane (5O / 5O wt .-%) - determined mixture at 3O ⁰ C. In addition, the curl, coefficient of friction and compression deformation recovery given in the following examples were determined as follows:

409 84 5/087

Ripple ^

I, number of crimps: A filament sample was cut into 25 ml long pieces under a load of 2 mg / d and subjected to a microscope (40 times) (η = 20: the observation was repeated 20 times and the mean value was converted into the
in the following tables) the number of
Counted ripples.

II. Degree of crimp: The degree of crimp was calculated from the observed values a and b according to the following equation: Degree of crimp = - ^ χ 100 (%), where a is the length of a filament loaded with 2 mg / d, b is the length after 30 seconds longer Mean load with 50 mg / d and the length of the filament without load was 25 mm (n = 10) _# .

Friction coefficient: __ A friction test device from Röder-3? Yp was used, in which ff the friction between
two filament fm R _e nce between filament and metal (hard chromium plating), and U ₃ (0) a static friction coefficient and αϊ-, (90) a dynamic friction coefficient at a speed of 90 cm / min,
rotating surface mean.

Compression deformation recovery j ^ 20 g of the loosened and opened fiber were left free for 3 days at 20 ° C and 65 % relative humidity, then the volumes a, b and c of the sample in a measuring box with a size of 150 mm χ 150 mm 500 mm was determined and the recovery from compression deformation was calculated from the following equation: degree of recovery = ^ r- χ 100 (> o), where a

a-D

the volume of the sample in the box under a loose lid weighing 46 g, b the volume of the sample after 1 hour compression by loading with 2700 g

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and c the volume of the samples 5 minutes after removal of the Mean pressure load. In the examples below The silicone compounds used were the following:

(1) dimethylpolysiloxane with at least two hydroxyl groups,

(2) Ix ₂ N-Ch ₂ CII ₂ -NiJ-CIi ₂ Ch ₂ CK ₂ -Si (OCh ₅ ) ₃ , (2 ¹ ) H ₂ N-Ch ₉ CL ₂ CL ₂ -Si (OCIi ₃ ) ₃ , (2 ") Ji ₂ N-Qi ₂ CiI ₂ Kn-CH ₂ Ch ₂ Ch ₂ (CIi ₃ ) Si (OCII ₃ ) ₂ ,

(3) kethylhydrogenpolysiloxane,

(4) CL ₃ Si (OQi ₃ ) ₃ ,

(5) Ch ₂ = ChSi (OCu ₃ ) ₃ ,

(6) CL ₀ -CH-CL ₉ OCh "Ch-Ch ₉ Si (OaI-O-

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Lsi s ii

Polyethylene terephthalate with an intrinsic viscosity / h 7 of 0.65 was melt-spun. After drawing in two stages, a yarn having a linear density of 300,000 denier (the linear density of a single filament was 6d) was obtained (Note 1). On the other hand, an emulsion of a silicone Verdi manure was prepared as follows: Folysiloxan (1) (n at 25 ⁰ C = 6 000 000 cSt) was emulgier't in a concentration of 30 wt .-% in Kasser with POE (8) and at the same -01eat The aminoalkoxysilane (2) was also emulsified in V.'asser in a concentrate of 20% by weight. A 10% aqueous zirconium acetate solution was prepared as a hardener. Immediately prior to use, the two emulsions and the acetate solution in an amount of 9.0 parts, 1.2 parts and 1.0 part, respectively, were mixed with 88.5 parts of V, water at room temperature to form an emulsion totaling 2, Contained 9% silicone compounds (preparation 1). In addition, using the compounds (2 ') and (2 ") in place of the aminoalkoxysilane (2), two emulsions (Preparations 2 and 3) having the same concentration of a total of 2.91 silicone compounds were prepared. These three emulsions were prepared by dipping on the polyethylene terephthalate fiber (the amounts adhered thereto were 0.28, 0.25 and 0.30 Geiv.-I, respectively, the amounts being determined as the difference between the dry weights of the coated and uncoated fibers) and then the fibers were left for 8 minutes heat treated at 160 ⁰ C, to cure the öbsrflache the applied film layers and curl without gleicnzeitig mecnanis caε crimp thermally V.'ege.

The three yarns treated in this way became filament to Filament made loose and could be cut off and without interference bundled (packed). Auäerderi ulieo inr üuerflaciienaussensn v.'äiirend the "7-day immersion in ί 3xane, foluene or xylene almost unchanged. The following coating agents were used to compare

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a to i and treated as indicated above. The observed results with respect to the curl and the coefficient of friction are summarized in the following table I like those of example 1 according to the invention.

The fibers produced by the erfindungsgemaiäen method and according to the comparative examples were in a Fnenol / tetrachloroethane (5O / 5O wt .-%) - dissolved Miscnung at 10O ⁰ C and the resulting solution was filtered durcn a glass filter, then the insoluble material in which it was Glass filter washed with ethyl alcohol and dried sufficiently. The obtained insoluble material composed of silicone compounds was subjected to a thermal analysis. The results obtained in carrying out the elementary analysis are summarized in Table II below, in which comparative example a is representative of the comparative examples. None of the fibers made by the methods in the comparative examples contained nitrogen.

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Tabel

I layering medium

oo απ ο

SiIicon connection

30 ^? oige emulsion of the compound (3) with a nonionic emulsifier

30 ^? Oige emulsion of the compound (1) pi ²⁵ Ή 6,000,000 cSt) with nonionic and anionic emulsifiers

Emulsion containing 27% of the compound (1) (p ^2b = 6,000,000 cSt) and 3% of the compound (4), with nonionic and anionic emulsifiers

catalyst

10 ^? dige watery
Zirconium acetate
sun it

Manufacturing process

Mixture of 3 parts of the emulsion, 0.3 parts of the catalyst and 96.7 parts Share IVasser

It

Emulsion containing Π% of the compound (1) / ^D 09 000 St) d 1% of the compound

n, nthaltend Π% s 6 009 000 cSt) and 1% (5) i ihii

dung (5), with non-ionic and anionic emulsifiers

Emulsion containing 27% of the compound (1) Cn ²⁵ = 6,000,000 cSt) and 5% of the compound (6), with non-ionic and anionic emulsifiers

Emulsion containing 27% of the compound (1) (Cn ²⁵ = 6,000,000 cSt) and 3S of the compound (3), with nonionic and anionic emulsifiers «I

ro ro

CD

cn

Tabel

(Continuation)

30% emulsion of the compound (1) (η ²⁵ = 6,000,000 cSt, high viscosity) with nonionic and anionic emulsifiers

Compound (1) sweet emulsion (η25 - 300 cSt, low viscosity) with a non-ionic emulsifier

usual finishing agent treatment agent)

(Surface mixture of 3 parts of the emulsion and 97 parts of water

Mixture of 3 parts of the Αρρ re tower message and 97 parts of Was s e r

K) O

cn

2A20151

In the above table, 2% polyoxyethylene octylphenol ether was used as the nonionic emulsifier and 1 % polyoxyethylene nonylpnenyl ether sulfate was used as the anionic emulsifier.

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Tabel

Examined
.J ^ i ^ enschaft
read chi cnt-
middle Frill lung Frizzy
degree of efficiency
0.
Ό Coefficient of friction V _d (90) f
U ₅ (O) - m
V _d (90) Upper compression
area redevelopment
smoothness (? o) 95 Preparation 1 At ζ at 1 of the
Krause 1
Number per
2.54 cn ' 13.7 f - f
V ₃ (0) 0.129 0.204 0.161 great 93 ¹¹ 2 9.1 13.8 0.181 0.130 0.193 0.174 great 96
78 "5
Comparison
example- a 9.0 14.0
14.1 0.175 0.121
0.195 0.187
0.283 0.175
0.290 . great -
very large
small amount 81 ^
80 O
co
co ¹¹ b
¹¹ c 6.9
9.0 12.9
12.8 0.177
0.248 0.190
0.173 0.280
0.244 0.271
0.240 small amount -
mediocre
'mediocre 83. '♦ 5/08 "d 9.3
10.1 13.5 0.236
0.214 0.151 0.267 0.255 ti 83 ' CU ¹¹ e 8.7 ■ 14.0 0.223 0.169 0.267 0.246 It 81 " ^£ 8.9 13.1 0.210 0.202 0.279 0.275 small amount -
mediocre 75 9.5 13.8 0.228 0.213 0.298 0.311 small amount 76 " H 9.0 13.5 0.251 0,201 0.305 0.294 It 78 ¹¹ i 9.1 14.5 0.245 0.238 0.315 0.330 ti 2420 ö, 9 O, 2Ö7

β)

ο ι

CXi

ω ei O

O τ-

II

- 22 -

to

LO

CM τ—

LO LO

4Y

(D to ^ + J ■ *

OT Ii O CJ <

cn

tn

OO

"3 ·

CTt

to

O - Ci O I CM τ— IO cn * - » Cj • # P! + J CM CM O O r-l O 0> CvS O «) ! —I «- <D «SP M. I. CM ■ r— • 5J- rH * ^ · {j Jt r— 1- O O (D O ,O Λ VD Ct OO i LO Lfi a C-- (U O I. O ■■ a O O • to ^ £ 3 LO (U to to to

O + J

c; it

υ c;

υ

to co

5- P!

(U O

CO r-C-

Ki H J

OK-rl

1- e

τ- CM IO

! Sl

Vi

r-l

Ci, Vi

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As can be seen from Table I above, the demonstrated The fibers produced by the method according to the invention are the "corpse Ripple on like those of the equivalency examples a ois i and besides they were with regard to the smoothness of the surface and the Compression deformation superior to these and their surface appearance or their grip (feel) hardly changed after the extraction with Tricnlene (Note 2). It was for sure on the formation of a strong film layer on the surface of the attributed to fiber according to the invention.

Note 1: The spinning process was carried out as follows:

The molten polyethylene terephthalate was extruded through a die having 250 nicely circular holes with two projections on a circular periphery of each hole and held at 300 ° C while the filaments were taken up at a speed of 680 m / l. In this spinning process, the spun filament was cooled immediately below the nozzle by means of an air flow of 4 m / second so Daih the two first projecting parts of each individual filament were quenched. The following stretching conditions were employed: using two hot water baths a Tenperatur within the range of 75-98 ⁰ C was carried out a 2-stage stretching in a Cesamtverstreckungsvernältnis of 3.10.

Note 2: About 5 g of the fiber prooe were placed in a Soxhlet extractor with 100 ml Trichlene for 4 to 5 hours extracted under reflux temperature. After drying the fiber was the frictional resistance (coefficient of friction) certainly.

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- 24 comparative example 1

As in Example 1, an aqueous solution was prepared which contained 2.91 silicone compounds consisting of 100 parts of polysiloxane (1) (η ²⁵ = 6,000,000 cSt) and 45 parts of aminoalkoxysilane (2), zirconium acetate being added as a karter became. After the emulsion had been applied to the synthetic fibers (synthetic fibers) produced in Example 1, the fibers were heat treated for 15 minutes at 140 ° C. in order to cure the silicone compounds with the formation of a solid film coating on them. The treated products showed discoloration in the form of yellow spots. Are solid felt cover of the silicone compounds vmrde as in Example 1 a Lleisentaranalyse subjected while the following results were eraalten: C = 45.0 wt S, L = 10.9 Gev.-% _t N = 4.1 wt -. ⁹ o, 0 = 1.2% by weight, the total content Λ was 61.2% by weight, the ascne content was 3S, i>% by weight.

Compare is pie1 2

In Example 1, an aqueous emulsion was prepared which contained 2.9% silicone compounds, consisting of 50 parts of polysilox ^ n (1) (n ²⁵ = 6,000,000 cSt), 50 parts of methylnydrogenpolysiloxane (η = 5,000 cSt) and 10 parts / ninoalkoxysilan (2 "), contained, wherein zirconium was added as a Hard After the application of the emulsion to the nergestellten in example 1, synthetic fibers, the fibers were 15 minutes at 140 ⁰ C for warrcebehandelt to the Silikonverbindun.ren under a Lildung. The named product had a somewhat lower surface smoothness and a somewhat poorer feel (to the touch) : C = 30.0% by weight ^? 5, i. = 7.9 Cew.-Έ, Ι * = 1.1% by weight, 0 = 0.5% by weight, total content Λ = 39.5 % By weight, As marriage content = ÖC, 5% by weight.

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Comparative example 3

In Example 1, an aqueous solution was prepared which contained 2.9% by weight of silicone compounds, consisting of 100 parts of polysiloxane (1) (n ²⁵ = 6,000,000 cSt) and 3 parts of aminoalkoxysilane (2), zirconium acetate being added as the harder became. After application of the emulsion to the produced in Leispiel 1 synthetic fibers, the fibers were 15 minutes at ⁰ C'wärmebehandelt 14G, the silicone compounds to form a solid FilmüDerzuges the same to hard. The treated product was inferior in its surface smoothness and in terms of aocipression recovery. That is, the surface smoothness was of medium quality and the compression recovery was 85% compared to that obtained with the fibers of the present invention. The felt cover made of the silicone compounds was subjected to an elemental analysis as in Example 1 and the following results were obtained: C = 35.9% by weight, H = 8.3% by weight, N = 0.8% by weight , 0 = 1.7 wt ^. ä, total genalt A = 46.7% by weight, ash content = 5 3.3% by weight,

Comparative example 4

As in Example 1, an aqueous emulsion was prepared which was 2.9 ^? ό Contained silicone compounds, consisting of 50 parts of polysiloxane (1) (η ²⁵ - = 6,000,000 cSt), 50 parts of methyl ^{hydrogen polysiloxane (n 2: j} = 5,000 cSt) and 55 parts of aminoalkoxysilane (2 "), with zirconium acetate added as hardener After the emulsion was applied to the synthetic fibers obtained in Example 1, the fibers were heat-treated at 14 ° C. for 15 minutes in order to wet the silicone compounds to form a solid film coating on the same vvar unsuitable for use as a commodity because it had a partially hardened part. The felt cover made of the silicone compounds was subjected to an elemental analysis as in Example 1 and the following results were obtained: C = 40.0% by weight, H = 11 , 3% by weight, N = 5.2% by weight, 0 = 1.1% by weight, total content A = 57.6% by weight, ash content =

42.4 wt. *. A-0984S / 0879

Example 2

Polyethylene terephthalate (η = 0.62} was melt-spun and, after drawing (Note 3), a yarn was obtained whose total denier was 100,000 denier (the denier of a single filament was 6d) Emulsion prepared containing 41 silicone compounds, consisting of polysiloxane (1) ( _n = 5,000,000 cSt) and aminoalkoxysilane (2), with zinc acetate being added as a larter. After applying the emulsion to the synthetic fiber by dipping (the amount of the fiber adhering silicone compounds was ü, 39 wt .-%), the fiber 5 »linuten at ISO wärmebehandolt ⁰ C to curl around the silicone compounds to a solid coating film on the same to hard, and to this. the crimp and the frictional resistance of the fibers thus obtained are shown in the following Table III In this case, the yarn used in Example 2 had a specific cross-sectional shape of each filament and exhibited accordingly end characteristic ripples with helical structures clockwise and counterclockwise. Since these structures were not changed by the treatment according to the invention, the product treated by the method according to the invention exhibited improved exchangeability. In addition, after the treated product was immersed in benzene and trichlene for 5 days, there was hardly any reduction in surface smoothness. A comparative example was carried out as in Example 2, but this time coating agent i was used. Results obtained are shown collectively in Table III below.

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Table III

Examined
Reading
medium Ripple lung O, re ibunaskoe fficient f - j
(0) n O, (90) Upper
surfaces
flatten Compression
sionser-
fetch Example 2 Number of frills
Ripple degree
Number per
2.54 cm -ό 8th O, f - f
V _d (90) 197 0, 160 great · 96
1 O
co
co Comparative
for example i 11.8 15, 2 1S2 0.126 O, 334 360 small amount 82 ι crt
"V.
O 11.8 16, 307 0.241 0, ro CO ■ NJ
CD co

Note 3

In order to carry out the spinning process, the molten polyester was extruded through a nozzle (The nozzle had 170 holes and each hole consisted of a main hole, the diameter of which was 1 and two small holes in the form of projections, the length of which was 0.6 and 0.4, respectively), an air stream being directed at the spinning filaments 10 to 20 cm below the nozzle outlet, to cool them, and the filaments were taken up at a speed of up to 905 m / minute. Then, using a hot water bath having a temperature of 75 ° C, the yarn became 2.30 times stretched to its original length.

Example 5

A yarn with a total denier of 90,000 denier (the denier of a single filament was 6 d) was prepared by spinning and drawing polyethylene terephthalate (η = 0.70). An emulsion was prepared which contained 4% silicone compounds, consisting of polysiloxane (1) and aminoalkoxysilane (2), and the same curing catalyst as in Example 1, and applied to the yarn by spraying (the amount adhering to the yarn of silicone compounds was 0.35% by weight) and then heat-treated ^{at 17C 0 C for 5 minutes.} The values observed in relation to the curl and the coefficient of friction of the product obtained are given in Taoelle IV below.

In addition, although the yarn used in this example remained the same circular cross-section as an ordinary synthetic fiber exhibited its bulkiness to a certain extent Obtained after treatment with silicone if it was mechanically crimped, and that after the heat treatment according to the invention The product obtained was easy to loosen without any action to loosen the filament prior to sizing

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Easy to open to separate filaments. The coefficient of friction of the final product was almost the same as that of a yarn with a non-circular cross-section and
a fiber obtained from a latent crimp. The end product changed its ligamentous scales after five days; eiri lintaucnen in Trichlene kaun.

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Table IY

Ripple

Examined

^ Properties

Le layering middle

Number of puckering peaks Degree

Number per

Z) j4 C] Ti &

Re i bun ^ s kpe ffiz ient

f - f
(0)

f - in

Compres * Upper sionser- surfaces fetch. smoothness (4)

O CO ■ <! (CO

Example 3

Comparative example i

9.1

12.4

11.0 x 0.197 0.151 0.183 0.177

11.5

Ü, 3Ü5

groio

0.294 0.350 0.34b low

73

Note 4: JJas Sxhmelzverspinnen was carried out by ^L: xtrudieren the molten polyester durcn a Üuse iTiit 4fc> circular punches at a temperature of 29o C and ⁰ riit receiving a rate of 770 n / minute. L-ie filaments were bundled into a yarn and stretched in two stages under \ ^? using two water baths stretched to 500 times their original length.

Example 4

In order to determine the relationship between the viscosity of the reactive polysiloxane and the ligaments of the harvested fibers, the yarn obtained in Example 5 and varying kinds of reactive polysiloxanes (1) having varying viscosities were subjected to various treatments. The results obtained are given in Table V below. In these cases the amount of adhesive on the fibers was about 0.4 wt silicone compounds ^f ₀

Table V "

viscosity Coefficient of friction £ u _d (90) f - m surfaces of the poly .0.144 P ₅ (O) y (90) smoothness siloxane
cSt y _s (of 0.166 0.220 0.160 at the
Feel 300 0, 190 0.150 O, 204 0.182 small amount 1,000 0.193 0.230 0.174 small amount 10,000 0.190 0.149 low-medium 0.228 0.172 moderate -250,000 0.190 0.148 mediocre - 0.147 0.225 0.169 great 5CO 000 0.189 0.130 0.220 0.166 great 5,000,000 0.1f> ö. 0.214 0.155 great 10,000,000 0.182 great

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From the above data it can be seen that the polysiloxanes with a viscosity greater than 250 COO cSt for the purposes of the present Invention give good results.

Example 5

25 Using the polysiloxane of Example 4 (η = 10,000 cSt) was the influence of the amount of polysiloxane on the final fiber product examined. It was found that the amount of polysiloxane in relation on the surface smoothness, preferably within the area from 0.2 to 0.6 bcw%; when using an amount above by this range the product became somewhat sticky and using an amount below this range the surface smoothness was insufficient.

Example 6

An acrylonitrile copolymer consisting of 88.8 parts of acrylonitrile, 5.8 parts of methyl acrylate and 5.4 parts of 2-methy1-5-vinylpyridine was wet-spun. After stretching, they were there obtained fibers (titer of a single filament = 10 d) cut into staple fibers with a length of 89 mm. On the other hand was an emulsion of silicone compounds created by mixing of the following components (A) to (D):

(A) 30% strength by weight emulsion of polysiloxane 6.30 parts (n ²⁵ = 5 COO 000 cSt) with two hydroxyl groups with POL (S) cleate as dispersant

(E) 20 rew .-% i, ee aqueous zirconium acetate - 0.63 parts solution

(C) Aminoalkoxysilane (2 ") 0.5 parts

(D) distilled in water 99.22 parts

409845/0 879

After the treatment of the staple fibers i.iit the emulsion, the fibers were 10 kinuten long oei wärniebcnandelt 13O ⁰ C, the silicone \ ^ a solid thin Filnüberzugs eruindungen under Ausbilduno- on denseloen too hard. The amount of silicone compounds adhering to the fibers was 0.60 Cew-o, based on the fibers. The treated product had an extremely good surface finish.

The treated fibers were dissolved in a dimethyl formamide solution and the insoluble material obtained in this way, consisting of silicone compounds. was subjected to an elemental analysis as in Example 1. The following results were obtained: C = 40.0% by weight, h = 6, δ-weight, - ^? i, N = 1.9% by weight, 0 = 2.1% by weight, total content A = 5% by weight ^? s, ash content = 50.0 wt ^. O.

Example ^ 7

Spun yarn of nylon 6 fibers (number'5 / fitor 52) that are yellow were dyed, were spun onto a woven fabric

2 made of polyester fibers with a number of 49 per ό, 45 an (square inch) tufted and cut to a stack length of 14 mm. After treating the tufted fabric with the emulsion used in Example 6, the fabric was kept at 130.degree. C. for 10 minutes heat treated. The treated fabric was attached to a backing fabric with rubber latex and a carpet was obtained. The carpet thus obtained had the same appearance or feel as natural fur.

Example 8

using polybutylene terephthalate spun yarn (Number 5 / titer 32) following the procedure of Example 7 was a carpet at ease. The carpet obtained had an appearance like wool and felt smooth * ie a fur.

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Example 9

Two kinds of. isotectic polypropylene with a different Molecular weights were spun and after drawing a yarn was obtained with a latent frizziness in which; the titer of a single filament was 6 d. After applying the emulsion used in Example 6 on the fibers Spray-on, the fibers were warn-treated at 140 G for 10 minutes, around the silicone connections to * a firm felt cover to harden the same, as well as to curl it, i.ie in Example 9 a comparative example was carried out, but this time under Use of the coating agent i and the resulting Results are reported collectively in Table VI below.

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Table VI

Properties examined I am very good at medium

Ripple

Number of curling · curling wheel

Number per

2.54 cm % coefficient of friction

f - f

W _d C90)

f - m

y _s (ü)

Surfaces smoothness

Compression recovery

4N example 9 ο

⁰⁰ Comparison-Jj example i

CD OO -J CO

11.2

11, 0

15.4

14.8

0.163 0.123 0.211 0.183 large

0.331 0.262 0.340

0.352 mediocre

71

Claims (12)

Claims Artificial fibers from a linear organic synthetic Polymer whose surface is coated with a silicone, characterized in that the silicone as structural elements carbon, hydrogen, nitrogen and contains oxygen, the content of nitrogen and the total content of these elements, determined by elemental analysis, in each case within the range from 1 to 5 or 10 to 60% by weight, based on the silicone, and that the silicone always has four characteristic absorption bands at a wavelength in the vicinity of 800, 1000 to 1100, 1260 and 3 4-50 cm, measured by infrared spectroscopy, having. 2. Synthetic fibers according to claim 1, characterized in that the total content of the S-structural elements is carbon, Hydrogen, nitrogen and oxygen in the silicone layer as determined by elemental analysis within the range of 4-5 to 55% by weight, based on the silicone. 3. Synthetic fibers according to claim 1, characterized in that the nitrogen content of the silicone layer is determined by Elemental analysis, is within the range of 1 to 3% by weight, based on the silicone. 409845/0879 4. Synthetic fibers according to claims 1 to 3, characterized in that they are (A) an organopolysiloxane with at least two hydroxyl groups and with a viscosity at 25 ⁰ C of at least 250 000 cSt of the general formula wherein E ^{1 is} a lower alkyl group and η is a value of 1.8 to 2.1, and (B) an aminoalkoxysilane of the general formula (CH_) 07. ι 3 m ZL R ^ E% (CH ₂ ) ₁ -Si- (OR ^q -) ₅ _ _m (2) wherein R is a hydrogen atom, a lower alkyl or aminoalkyl group, Ir is a hydrogen atom or a lower alkyl group, R is a lower alkyl group, 1 is an integer and m is the number 0 or 1, applied in the form of an emulsion, are coated. 5. Synthetic fibers according to claim 4, characterized in that the emulsion is 0.1 to 20 wt .-% of the organopolysiloxane (A) and from 0.001 to 6% by weight of the aminoalkoxysilane (B). 6. synthetic fibers according to claim 4 or 5 »characterized in that that the viscosity of the organopolysiloxane at 25 ° C at least 5OO. 000 cSt. 40 9845/0879 - Jo - 7. Synthetic fibers according to Claims 4 to 6, characterized in that the silicone applied in the form of an emulsion _{adheres to the fibers in an amount of from O 1} OI to 2% by weight, based on the fibers. 8. synthetic fibers according to claims 4- to 6, characterized in that that the silicone applied in the form of an emulsion to the fibers in an amount of 0.1 to 0.7% by weight, based on the fibers, adheres. 9. synthetic fibers according to claims 1 to 8, characterized in that that the polymer is selected from the group of polyesters, polyamides and polyolefins. 10. A method for the production of synthetic fibers, the surface of which is coated with a silicone, characterized in that that a silicone is used, the structural elements carbon, hydrogen, nitrogen and oxygen contains, the content of nitrogen and the total content on these elements, determined by elemental analysis, in each case within the range from 1 to 5 or 40 to 50 % By weight, based on the silicone, and that the silicone always has four characteristic absorption bands at one Has wavelengths in the vicinity of 800, 1000 to 1100, 1260 and 3 ^ 50 em as measured by infrared spectroscopy, wherein the fibers after drawing with an emulsion be coated, which contains (A) an organopolysiloxane 409845/0879 with at least two hydroxyl groups and a viscosity at 25 ^° C. of at least 250,000 cSt of the general formula ^E 'n ^Si0 (4- _n ) / 2 wherein R ^{1 is} a lower alkyl group and η is a value of 1.8 to 2.1, in an amount of 0.1 to 20% by weight and an Aniinoakoxysilan of the general formula 2, <? Vm TpM (CH) Si (OR ^ ₁₁₁ (2) wherein R is a hydrogen atom, a lower alkyl or aminoalkyl group, R ^ is a hydrogen atom or a lower alkyl group, R is an IT-lower alkyl group, 1 is an integer and m mean the number 0 or 1, in an amount of 0.001 to 6% by weight and a hardener in an amount of 0.01 to 2% by weight , each based on. the fibers, and then subjecting the whole to a heat treatment at a temperature of from 0 to 200 ° C to harden the coated fibers. 11. "The method according to claim 10, characterized in that the coated fibers are crimped by the heat treatment will. 409845/0879 12. The method according to claim 10 or 11, characterized in that a temperature of 140 to 180 ⁰ C is used in the heat treatment. 13. Process according to claims 10 to 12, characterized in that a treatment time of 2 to 20 minutes is used for the heat treatment. 409845/0879