EP1192310A1

EP1192310A1 - Method for dying and brightening synthetic and cellulosic fibers

Info

Publication number: EP1192310A1
Application number: EP00952969A
Authority: EP
Inventors: Thomas Martini; Jochen Stock; Theodore Samuel Thornburg; John Balekdjian; Mean-Jeng Hou
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 1999-06-10
Filing date: 2000-06-02
Publication date: 2002-04-03
Also published as: BR0011730A; WO2000077291A1; MXPA01012688A

Abstract

The invention relates to a method for continuously brightening or dying synthetic fibers or cellulosic fibers by bringing an optical brightening agent or a dye and a fiber preparation agent into contact with the fibers to be brightened or dyed, and by subsequently heating these fibers to a temperature of at least 100 °C.

Description

Process for dyeing and lightening synthetic and cellulosic fibers

The present invention relates to a continuous process for dyeing and lightening synthetic or celio fibers, and the fibers thus produced. Dyes and / or optical brighteners are applied to the fiber directly during the spinning process in combination with fiber preparation agents.

The dyeing and optical brightening of filaments and staple fibers is mainly practiced in three ways.

In the so-called lightening or dyeing of the spinning mass, the optical brightener or the dye is added during polymer production or generally before the fiber is spun. So z. B. the optical brightener or dye introduced during polyester fiber production during the transesterification or polycondensation. The addition before spinning is often carried out using a masterbatch, i. H. a multiple concentrate of the brightener or dye in polyester. 1 - 20% brightener or dye settings are used, which then by

Mixing processes are homogeneously distributed in the polyester mass before spinning. In the case of polyamides (PA) or polyurethanes (PU), the brightener or dye can be pre-dissolved in a monomer component and then the polymerization process can be carried out. When lightening or dyeing polyacrylonitrile (PAN), the brightener or dye is dissolved together with the polymer in an aprotic polar solvent (e.g. in DMF, DMSO, DMA or DMC). The dissolved mass is spun through nozzles into a hot air chamber, whereby the solvent evaporates.

In the textile industry, the lightening or dyeing of fabrics or knitted fabrics made from filaments or staple fibers is carried out in the so-called block thermosol process or exhaust process. In the block thermosol process, the textile fabric is predominantly used with a diluted, brightener or dye-containing dispersion, emulsion or solution, squeezed between rollers and heated to 160 to 220 ° C for 40 - 15 seconds to fix the brightener or dye.

In the exhaust process, the optical brightener or dye is applied to the fiber from an aqueous medium at a ratio of about 1: 5 to about 1:40 at 90 to 130 ° C. Filaments and staple fibers can also be lightened directly using the same process.

Other methods of lightening or dyeing, such as pad steaming, pad washing, pad dwelling, are related and can be found in the literature for interpretation. DD-104 325 describes a process for lightening polyester which is characterized in that immediately after the shaping process, i.e. Spinning and solidification process, the fiber structure obtained is treated with a dispersion of optical brighteners in water, if appropriate in combination with hydrophilic liquids or preparation agents, and the spinning material is subjected to storage in containers for several hours before being drawn into the fiber raw material. These prior art processes are characterized by the following disadvantages:

• In the case of polymer spinning material lightening, relatively large amounts of brightener must be used, because in order to achieve the desired white effect on the fiber surface, the entire fiber cross-section or the entire fiber mass must be colored or lightened. However, only the remission of the outer fiber cladding is responsible for the white effect of the fiber. Furthermore, this process is characterized by low flexibility with regard to the requirements with regard to whiteness and nuance, since only relatively large quantities of fibers can be lightened for process engineering reasons. • The change from lightened material to lightener-free material is also associated with a time-consuming and costly cleaning process, since lightening residues are difficult to remove. • Lightening or coloring using masterbatch technology requires additional work steps such as. B. the production and precise dosing of the masterbatch. In addition, as in the case of lightening or dyeing in polymer synthesis, a total lightening or dyeing of the fiber cross section is carried out.

• Due to the long-term temperature load at the PES manufacturers, only brighteners with high temperature resistance and low volatility in glycol can be used.

• The textile lightening processes are costly and time-consuming processes with high water and energy consumption, and corresponding economic and ecological disadvantages. Furthermore, in order to achieve appealing white effects, high amounts of brightener are also used, since the brightener has to penetrate deep into the fiber in order to achieve good fastness properties. Indications for the amounts of brightener used are 100 to 300 ppm in the spinning mass process, while in the textile lightening process between 100 to

1500 ppm optical brightener can be used in its active form (i.e. 100%).

• The process described in DD-104325 cannot be integrated into the continuous fiber production and processing process due to the long storage time required for the brightener-containing molded article and is therefore of no technical significance. In addition, very high amounts of optical brighteners are used.

It has now surprisingly been possible to show that highly brilliant and high-fast brightening and dyeing effects are achieved if the brightener or dye is applied together with the fiber preparation and fixed by brief heating in the normal fiber production process. It was surprising that you can achieve white effects with small amounts of brightener, the z. B. in the dope process can only be achieved with a multiple amount of brightener. Likewise, according to the inventive method

Using the same amount of brightener achieves better effects than in the exhaust process. The invention thus relates to a process for the continuous lightening or dyeing of synthetic fibers or Celiosis fibers by one optical brightener or a dye and a fiber preparation agent in contact with the fibers to be lightened or dyed, and then heating these fibers to a temperature of at least 100 ° C.

Another object of the invention are colored or, in preferred

Embodiment, lightened fibers that can be produced by this method. The fibers of the invention carry dyes or optical brighteners only in a limited area near the fiber surface, but not in the fiber core. The fibers are therefore not thoroughly interspersed with dye or optical brighteners, but rather they comprise a colored or lightened part on the outside and a non-colored or barely colored or lightened part in the core. The latter is also referred to as a weak fluorescence core. In preferred embodiments of the fiber according to the invention, the low-fluorescence core has a diameter of 10 to 90, particularly preferably 30 to 80, in particular 50 to 75% of the fiber diameter. In a preferred embodiment, the low-fluorescence core contains at most 30, particularly preferably at most 0.1 to 10% by weight of the total amount of optical brightener on the fiber.

Preferred synthetic fibers are polyester fibers, polyacrylonitrile fibers (PAN),

Polyamide fibers (PA), polyurethane fibers (PU), polypropylene fibers, viscose fibers and mixtures of these fibers with each other.

Fiber preparation agents are an indispensable aid in the production of synthetic or cellulosic fibers. It is about

Products that are applied to fibers during the manufacture to enable subsequent processes such as drawing, twisting, warping, texturing and spinning. A description of the application options for fiber preparation can be found in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A26, p. 238 ff. The term preparation agent is therefore often used to mean the products of this textile further processing, such as lubricants, rinsing, warping or twisting oils or general finishing agents. This results in the following classification for fiber preparation agents: 1. Preparations for fiber production

a) Preparation for filaments (continuous filaments) b) Preparations for staple fibers

2. Finishing agents for further processing (as described above)

The fiber manufacturer's technical requirements for fiber preparation products can be briefly outlined as follows:

• imparting good sliding properties (i.e. optimally adjusted fiber / metal friction)

• Good antistatic properties

• Avoiding capillary swirls and promoting a good bobbin build (i.e. appropriate adjustment of the thread / thread adhesion and the thread closure).

However, the points mentioned are only the most important of the properties to be set, which are typical for fiber preparation agents. There are also a number of secondary properties that are also essential for the proper functioning of a fiber preparation.

• Non-corrosive (especially for metallic workpieces and machine parts) • No promotion of bacterial growth (in the best case bactericidal

Characteristics)

• High thermal resilience

• Easily washable or removable from the fiber

• Ecological harmlessness • Homogeneous distribution of the fiber preparation on the thread and good wettability • avoidance of interactions with the fiber (such as oligomer retention)

• Easy handling of the fiber preparation agents (such as low viscosity) and the corresponding fiber preparation baths

The fiber preparation system is applied to the surface of the fiber using various methods, the most important of which are as follows:

• Thread guidance through an immersion bath • Application by means of an immersion roller

• Application via a "dosing pin" ("pin application") with feeding through a dosing pump

When applied as an aqueous emulsion, this is usually done at ambient temperature. Depending on the viscosity of the preparation used, Neat Oil applications require application temperatures of approx. 50 - 60 ° C. In the further course of the fiber processing process, the preparation on the fiber is partially exposed to significantly higher temperatures. Stretching processes always take place above the glass point, usually approx. 140 - 160 ° C for polyester. Highly drawn filaments often even go to processing temperatures just below the melting point of polyester, i.e. to approx. 250 to 260 ° C. Modern high-temperature heaters in texturing expose the fiber material to temperatures of 550 ° C and above for a short time.

Although one-component systems are still known today, it is obvious that the multitude of desired properties can usually only be met by using mixtures of several components. The requirements of the fiber-producing industry are offset by a corresponding number of components in the chemical industry that are used in the production of fiber preparation agents. In terms of application technology, the components can be classified as follows: a) lubricants b) antistatic agents c) emulsifiers d) other additives

The properties of the fiber preparation system are predominantly dominated by the first three compound classes a) - c). Additives such as Corrosion inhibitors often play a subordinate role, but are indispensable from case to case. The aim is often to control the entire requirement profile using as few components as possible.

a) Lubricant

Lubricants are substances that control the tribological properties of the fiber preparation system. The main thing is the friction between the capillaries (so-called thread-thread adhesion or

Thread closure) and the adjustment of the friction on different metallic machine parts (thread-metal friction). Other materials are also used in fiber production (especially when texturing POY filaments) such as Polyurethane, ceramic materials and plastic straps (such as so-called "Murata belts"). Chemically, until a few years ago, the lubricants were mainly based on paraffinic mineral oils, so-called highly purified "white oils". Silicone oils are also often used here. For technical and ecological reasons, synthetic esters have recently been increasingly used (predominantly based on natural ones

Fatty acids). On the other hand, applications that aim to increase the friction rather than lower it (e.g. in the texturing of POY filaments) often require polyalkylene oxides such as Copolymers of ethylene oxide and propylene oxide. Of course, mixtures of the corresponding components are also common here.

b) antistatic agents

In fiber production, the fibers are made with considerable Speeds pulled across different materials (eg over "thread guiding elements" or heated metallic rollers). This creates considerable electrostatic charges. The resulting discharges represent an important potential hazard due to the formation of sparks. Chemically, polar compounds, in particular electrically charged, ie ionic compounds, are used to avoid electrical charges. The following substance classes are widespread:

b1) phosphoric acid esters resulting from the reaction of hydroxyl groups

Compounds with phosphorus pentoxide (P ₂ O ₅ , more precisely PO ₁₀ ) are obtained. The acid groups remaining on the phosphorus atom are at least partially neutralized with lye (e.g. NaOH).

b2) phosphoric acid esters resulting from the reaction of hydroxyl groups

Compounds with phosphorus oxychloride (POCI ₃ ) can be obtained. The acid groups remaining on the phosphorus atom are at least z. T. neutralized with lye (eg NaOH).

b3) long-chain amine oxides of the type:

CH '3,

(where n = 5-22)

b4) organic compounds containing sulfo groups, such as e.g. sulfonated oils and

Fats. The acid groups remaining on the sulfur atom are at least partially neutralized with lye (e.g. NaOH).

b5) generally quaternized amines with different chemical structures Since these are always electrically charged or at least strongly polar compounds and the lubricants presented in group a) are predominantly non-polar in nature, emulsifiers are often used to produce homogeneous mixtures of the two classes of substances. This applies both to the application of fiber preparations as an aqueous emulsion and in bulk (so-called "Neat Oil application").

c) emulsifiers

In principle, all surfactants and their preparations can be used as emulsifiers. These are e.g.

Oxalkylation products of fatty acids, fatty acid amides, fatty alcohols, fatty amines or alkylphenols: Various fatty acid condensation products, alkyl or alkyl ether phosphates and sulfonated oils and fats can also be used. Generally speaking, the number of emulsifiers available is arbitrarily large. When selecting the corresponding substances, however, it must be taken into account that the emulsifier must "match" its lubricating properties, i.e. its effect is not impaired, but may even be supported. The emulsifier must neither influence the fiber material nor contact materials such as Change texturing or friction discs chemically or mechanically (e.g. by swelling). For these and many other reasons, alkoxylation products as enumerated above have largely become established today. It should be noted that the antistatic substances mentioned in group b) can also have emulsifying properties.

d) Other additives

Others such as corrosion inhibitors, thermal stabilizers, yellowing stabilizers or bactericides play a subordinate role, since such additives often have the complicated interplay described above

Disrupt components in groups a) to c). This can lead to disturbances in the dispersed particles, such as abrasion or instability of the dispersions. It was therefore surprising that dyes and optical brighteners can be introduced into a fiber preparation system in high concentrations, and that it is possible in this way to achieve highly brilliant and high-fast lightening and dyeing effects. It has been shown that under normal application conditions, as is customary in the preparation of fibers, permanent lightening or coloring can be achieved. Excellent white effects are achieved both when applied with a dosing pen and in an immersion bath at a contact temperature (godet) of 190 ° C (residence time 4 sec) without affecting the friction properties of the preparation system. The preferred temperatures here are also fiber-dependent. In the case of polyester, these temperatures are between 100 and 220 ° C., preferably between 130 and 200 ° C., very particularly preferably 190 ° C. In modern high-temperature heaters, the fiber material can be exposed for a short time at temperatures of 550 ° C and higher, with exposure times in the 1/10 second range and below.

Preferred temperatures for polypropylene are 160-280 ° C, for polyamide 130-170 ° C.

For polyacrylonitrile and viscose fibers, temperatures of 100 -

120 ° C preferred.

Normally, the thermosetting of PES brighteners requires fixing times of 15 to 40 seconds at temperatures of 160 to 220 ° C to fix the brightener in the fiber. The through the conventional

As already indicated, brightening amounts of application methods applied are approximately 100-1500 ppm in order to achieve sufficient white effects or a full white, while 100-300 ppm are used for the purpose of lightening the dope. Surprisingly, it has now been found that in the method according to the invention already with

Concentrations of, for example, 35 ppm brightener or dye (with respect to active substance) effects can be achieved which are conventional Process can only be achieved with a multiple of this amount of brightener or dye.

All commercially available textile brighteners or dyes for synthetic fibers are suitable as optical brighteners or dyes. For example, these products can be provided with dispersants or, in the case of water- or solvent-soluble products, added to the preparation in dissolved form. The composition of the dispersing agent is not critical, but it must not cause any precipitations or separations with the preparation system. The commercially available dispersion brighteners or water or solvent-soluble types meet these requirements. Suitable optical brighteners or dyes for the process according to the invention are nonionic polyester brighteners or dyes, anionic PA or viscose brighteners or dyes or cationic polyacrylonitrile brighteners or dyes.

Nonionic brighteners or dyes can produce excellent white effects on polyamide or polyolefin fibers. The optical brighteners or dyes can be used alone or in mixtures, and synergistic effects can also occur. Brighteners or are suitable for the process according to the invention without restriction

Dyes with the following structures:

Nonionic brighteners of formulas (1) - (8):

d)

wherein R 1 and R ₂ independently of one another are H or (-CC ₆ ) alkyl, A = N or C and X are a bond via 1,4 naphthyl, 2,5-thiophene, 2,5-furan, 1, 4-phenyl, ethylene, stilbene, styryl or imidazolyl units; where X = O or S, R ₃ in the 5-position is an H or Cl atom, a methyl or phenyl group and R _{4 is} an H atom, or R ₃ and R _{4 are} both a methyl group in 5, 6 or 5 , 7-position, n = 0 or 1 and B is a cyano or carbo (d-C4) alkoxy group or a group of the formulas:

mean, wherein R ₅ (CC ₆ ) alkyl, (CC ₆ ) chloroalkyl, (C ₁ -C ₄ ) alkoxy- (C ₁ -C ₄ ) alkyl, hydroxy- (-C-C4) alkyl or a group of the formula - (CH ₂ CH2θ) _n -R, with n = 2 or 3 and R = hydrogen or (CrC ₄ ) alkoxyphenyl, R ₇ = (C -C ₄ ) alkyl and R ₈ = cyano- or carbo- Mean (CrC) alkoxy;

(3) the CN groups may be the same or different in the o, m, p position;

(5)

wherein R _{9 is} hydrogen or alkoxy, Rio alkoxy and Rn alkyl, alkoxyalkyl or dialkylaminoalkyl;

(6) (6a)

where R ₁₂ = phenyl or the group of the formula:

and R _{13 is} one of the groups of the formulas:

mean.

COO- (C ₁ -C ₆ ) alkyl

(8th)

Anionic brighteners, which are particularly suitable for polyamide and viscose, correspond to formulas (9) to (23b):

where R is independently OH, NH ₂ , 0- (CC ₄ ) alkyl, O-aryl, NH- (CC ₄ ) alkyl, N - ((CrC ₄ ) alkyl) ₂ , N - ((-Cι- C ₄ ) -alkyl) - ((C ₁ -C ₄ ) -hydroxyalkyl), N - ((-C-C ₄ ) - hydroxyalkyl) ₂ , NH-aryl, morpholino, S- (CrC ₄ ) -alkylaryl or Cl and M represents Na ⁺ , K ⁺ , NH4 ⁺ or NH _(4-a ) R _a , where a = 1, 2 or 3 and R = dC ₄ -hydroxyalkyl, in particular C ₂ -hydroxyalkyl, the stoichiometric indices of the sulfonate groups depend on the nature of the radical R, namely on how many such groups can carry this radical;

(10)

where AP _I and Ar _{2 are} independently substituted or unsubstituted aryl and R ₁₅ and R ₁₅ ', which may be the same or different, are hydrogen, (CC ₄ ) alkyl or phenyl;

(11)

in which Ar ₃ and Ar ₄ independently of one another are phenyl, diphenyl or naphthyl radicals, the further substituents such as hydroxyl, (-CC ₆ ) -alkyl-, (Ci-CβJ-alkoxy, halogen, hydroxyalkyl, amino, alkylamino -, Acylamino, carboxyl, alkoxylcarbonyl, sulfonic acid, sulfonic acid ester, alkylsulfonyl, arylsulfonyl, sulfonyl and sulfonamide groups;

wherein R _{16 is} halogen or (-CC ₆ ) alkyl, R _{17 is} a substituted or unsubstituted (CrC ₆ ) alkoxycarbonyl, (CrC ₆ ) alkylsulfonyl, sulfonamide or sulfonic acid group with M = 0; 1 ; Represent 2 or 3;

(12a) (12b)

(12 c)

(13)

(14)

With R ₁₈ = H, alkyl, oxalkyl, halogen, CN, COO- (CC ₄ ) -alkyl or CO-N [(CC ₄ ) -alkyl] ₂ and n = 0 or 1;

wherein n = 0 or 1;

(17)

(19)

(20)

(22)

(23) wherein the sulfonate groups can be located at any position on the aromatic systems.

Nonionic brighteners for polyamides correspond to formulas 23a, 23b or formulas 1-8.

S0 ₂ - CH ₂ - CH ₂ - OH S0 ₂ - CH ₂ - CH ₂ - OH

(23a) (23b)

The cationic optical brighteners are compounds of formulas with a pyrazoline basic structure, which are in the salt form, that is to say acid addition salts. Suitable acids for this are those that have colorless anions, such as. B. CrC ₃ alkanoates, CrC4 alkane phosphates, C1-C4 alkanesulfonates, C ₂ -C ₃ hydroxyalkanoates, alkanesulfonates, phosphite, sulfamide, halides, methosulfate, p-toluenesulfonate, preferably those which have good water solubilities. This also includes compounds of the formulas (24) to (30): wherein Ar ₅ and Ar _{6 are} independently substituted or unsubstituted aryl and R _{19 is} hydrogen, CrC ₄ alkyl or phenyl.

In which Ar ₇ and Ar ₈ independently of one another are phenyl, diphenyl or naphthyl radicals which represent further substituents such as hydroxy, CrCβ-alkyl, C ₁ -C ₆ -alkoxy, halogen, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl , Alkoxycarbonyl, sulfonic acid, sulfonic acid ester, alkylsulfonyl, sulfonyl and sulfonamide groups, and R _{19 has} the above meaning.

Compounds of the formula:

wherein R ₂ o is hydrogen, halogen or CrCβ-alkyl, R _{21 is} a substituted or unsubstituted CrCβ-alkoxycarbonyl, -CC ₆ -alkanesulfonyl, sulfonamide or sulfonic acid group, m = 0; 1 ; 2 or 3 mean and R _{19 has} the above meaning.

Compounds of the formula:

(27)

where A is a group of the formulas:

means and in which R _{22 is} substituted or unsubstituted Ci-Cβ-alkylene, CrC ₆ - alkylene-O ^ CrCeJ-alkylene ^ CrCe alkylene-CONH ^ Ci-CeV alkylene, (Cι-C ₆ ) - alkylene-CONH- (CrC ₆ ) - Alkylene, -NH- (C ₂ -C ₄ ) alkylene or (C ₂ -C ₄ ) -hydroxyalkylene- NH-

(C ₂ -C ₄ ) Hydroxyalkylene, R ₂₃ independently of one another hydrogen, (-CC ₆ ) alkyl, (C ₂ -C ₆ ) hydroxyalkyl or two radicals R ₂₃ together with N atom a morpholino, pyrrolidino -, piperidino, N-alkylpiperazino or N-hydroxyethylpiperazino group, R ₂₄ and R ₂₅ independently of one another are hydrogen, methyl or chlorine, R _{19 has} the meaning given above, n = 0 or 1 and X is a colorless anion.

The most common pyrazoline brighteners are the compounds of the following formula:

(28)

wherein A represents a 4-chlorophenyl group and R _{26 represents} a group of the following formulas: -NH ₂ , -C ₂ H4N (CH ₃ ) ₂ , -CH ₂ CHCH ₃ N (CH3) 2, -C ₂ H ₄ OC ₂ H4N ( CH3) 2,

-CH (CH ₃ ) CH ₂ N (CH ₃ ) ₂ or A is a 2-methyl-4,5-dichlorophenyl group and R ₂ 6 is a group of the formula -C ₂ H ₄ N (CH ₃ ) 2, (CH ₂ ) _x -OCOR ₂ 7 or (CH ₂ ) x-OCOR ₂₈ , x is a number from 1 to 4, R ₂ C Cβ, preferably C ₁ -C ₃ -alkyl or Ci-Cε-, preferably CC ₃ -hydroxyalkyl, R _{28 is} hydrogen or -CC ₆ -, preferably CrC ₃ alkyl. Suitable Ci-C _δ alkyl radicals are unbranched and branched alkyl radicals, such as the methyl, ethyl, propyl, butyl, pentyl and hexyl radical. The same applies to the -C ₈ alkoxy groups and for the -C ₆ alkylene groups.

Other compounds of a cationic nature are benzimidazole-benzofuran derivatives or benzimidazole-benzoxazole derivatives of the general formula:

where X = N, or CH and R ₂₉ Cr rAlkoxy, R ₃₀ and R ₃₁ independently of one another dC ₄ alkyl and An ^" for a colorless anion as described above.

Other compounds of a cationic nature are based on coumarin.

(30)

wherein R _{32 can be} hydrogen, halogen or CH ₂ COOH, R _{33 can be} hydrogen, phenyl, COO- (CrC ₄ ) -alkyl or a group of the following formula:

CH,

+ / ^ = N

N

N and R ₃₄ 0- (CrC ₄ ) -alkyl, N [(CrC ₄ ) -alkyl] _2l NH-CO- (CrC ₄ ) -alkyl or a group of the formulas

where R ₃ , R ₃₈ and R ₃₉ independently of one another are hydrogen, C 1 -C 4 -alkyl or phenyl. The use concentrations of optical brighteners can surprisingly be very low. In relation to the preparation mixture, clear whitening effects can be achieved with 0.01% commercial brightener mixtures or 0.001% active substance.

example 1

Yarn used: The example describes the preparation of a polyester yarn with a

Fiber titers of 167 f 64 and a Ti0 ₂ content (A-Type) of 0.4%.

Preparation mix used:

The preparation is made up of 75 parts of Afilan V 4657 (as Afilan ^® V 4657 30%

Contains active substance, this corresponds to 22.5 parts of active substance), 17.5 parts of water and 7.5 parts of Afilan V 4760. This preparation mix

5 parts of a dispersed brightener mixture added:

The dispersed brightener mixture consists of 4.9% of the brightener of the formula:

and 2.1% of the brightener of the formula:

8.5 g of the mixture thus obtained are weighed out and made up to 400 g with water. This mixture is used to fill the immersion bath described below.

Application:

The total mixture thus obtained is applied by the following method: the thread is drawn off from a bobbin with preparation-free polyester yarn (as described above) at a constant speed of 70 m / min. The thread is passed over a total length of 15 cm through an immersion bath which contains 400 g of the mixture described above.

The thread wetted in this way is passed between contact surfaces and squeezed off. For drying, the yarn is passed several times over a godet heated to 190 ° C. in such a way that the total contact time is 4 seconds. The yarn is then wound up and fed to the white effect determination and the analysis of the brightener content.

The amount of brightener determined on the fiber by dissolving and UV spectrometry is 35 ppm. The whiteness effect achieved - determined according to the Whole / Semolina method - is 161 whiteness units. The white effects are washable and show a lightfastness of 6 - 7 (according to DIN 54004). The running properties and coefficients of friction of the fiber do not affect further processing.

Example 2:

In comparison to Example 1, a lightening was carried out in the polyester spinning mass. The brightener is added in the polycondensation stage.

1000 g dimethyl terephthalate (DMT) 720 g ethylene glycol

0.23 g manganese (II) acetate

are introduced into a 2 l flask equipped with a VA stirrer, a 20 cm packed column and a cooler system. The heating bath is heated to 160 ° C., after the DMT has melted, the stirrer is started and the apparatus is flushed with a stream of N2.

After the methanol has started to be distilled off, the temperature is increased every 15 minutes by 10 ° C. to 230-235 ° C. and kept at this level until all of the methanol has been distilled off.

0.3 g Sb ₂ 0 ₃ 0.09 g H ₃ P0 ₃ 4.0 g Ti0 ₂ (A-Type)

and 0.1 g of a brightener of the formula:

dispersed in ethylene glycol into the 2 l flask, which is now equipped with a condenser for glycol distillation and with a vacuum pump. The bath temperature is raised to 250 ° C and the flask is flushed with pure nitrogen. As soon as the viscosity of the flask contents allows, stirring is started. After the transesterification product has melted completely, the N ₂ stream is interrupted and the following polycondensation program begins:

15 min at 799 mbar 15 min at 532 mbar

15 min at 266 mbar 15 min at 133 mbar 15 min at 60 mbar 15 min at 13 mbar

This process is supplemented by increasing the temperature to 250-270 ° C. under a vacuum of at least 0.013 mbar, the stirrer speed being kept constant at 180 rpm. After the desired viscosity is reached, the heating system is removed and the piston, which is blown up during cooling, is protected accordingly.

The polyester mass is broken hydraulically and ground after CO ₂ cooling. The material is dried for 5 hours at 120 ° C. and spun. The whitening effects of the spun fiber according to the method / semolina amount to 160 whiteness units.

Example 3:

The procedure is as in Example 1. However, a dispersed brightener mixture is used, each consisting of 1% of the brightener of the formula:

and 5.5% of the formula:

Excellent white effects with a light fastness of 7 were achieved (DIN 54004).

Example 4:

The procedure is as in Example 1. A dispersed mixture of 8.0% of the formula is used as brightener:

and 15% of the formula:

for use. The analytically determined amounts of optical brightener mixture are 75 ppm. The measured degrees of whiteness according to Ganz / Grießen are 158. The brightening effects are washable and a lightfastness of 5 - 6 (DIN 54004) is obtained.

Example 5:

The procedure is as in Example 1. 10% of a dispersion with 20% active content of the formula:

used. Very good whitening effects with a whiteness of 158 were achieved using the whole / semolina method. The fiber contains 160 ppm of the optical brightener.

Example 6:

The polyester yarn used in Example 1 is lightened at 130 ° C. for 45 min in a bath with a liquor ratio of 1:20 with 0.08% (160 ppm) of the brightener from Example 5 in such a way that the brightener practically quantitative from the bath the fiber is drawn. After rinsing and drying, a whiteness after whole / semolina of 153 is achieved.

Example 7:

As a fiber preparation, a commercially available flat yarn preparation for polyester and nylon filaments (Afilan 4097) is diluted with water to an active content of 10%. Preparation-free polyamide 6 with a titer of 220 f 40 is used. The application is carried out as described in Example 1, but the godet temperature is reduced to 150 ° C. Based on the amount of preparation used (active content), 10% of a 10% aqueous setting of the brightener of the formula:

used. The pH of the application bath is in the neutral range. The amount of brightener applied to the fiber is 217 ppm of active substance with a very good white effect. Similar effects are obtained at pH 5.5.

Example 8:

The procedure is as in Example 7. An optical brightener of the formula is used:

in 13% dispersion. Very good lightening effects were achieved. The amount of brightener absorbed by the fiber is 120 ppm of active substance.

Example 9:

Example 1 is used. However, 10 parts of the disperse dye ^Foron® Brillantviolettt S-3RL are added to the preparation mixture. A uniformly brilliant violet-colored fiber is obtained. The coloration is washable. Example 10:

The commercially available preparation components Afilan AP and Afilan GD are mixed in a ratio of 1: 2 and the mixture is diluted with water so that a 10% emulsion is obtained. For this purpose, 0.65% of a commercial setting (approx. 15% active content) of the brightener:

HCOO

CH3

A preparation-free polyacrylic fiber with a titer 330 f 100 is selected as the fiber material. The godet temperature is 120 ° C. The application is otherwise as described in Example 1, the liquor absorption about 100%. Then there are 55 ppm of optical brighteners on the fiber, which have a clear brightening effect.

Example 11:

The preparation mixture described in Example 1 is mixed with 1.0 g of the dye Nylosan ^® Blue FL 150 instead of the brightener and adjusted to pH 5.4 with 10% acetic acid with stirring. Otherwise the procedure is as in Example 7. An intensely blue-colored fiber with good fastness properties is obtained. Example 12:

The procedure is as described in Example 1, but unsplit, washed viscose fiber, dtex 200, is used. A 10% stock preparation from the commercially available products Leomin HSG-R and Leomin WG in a ratio of 60:40 is used as the preparation agent. which contains 5% of the optical brightener Leukophor BMB liquid. (Medium affinity DAS derivative) The contact time on the godet is 4 seconds at 120 ° C. A whiteness increase of 40 whiteness units according to the formula of Ganz is achieved.

Claims

claims

1. A process for the continuous lightening or dyeing of synthetic fibers or Celiosis fibers by bringing an optical brightener or a dye together with a fiber preparation agent into contact with the fibers to be lightened or dyed, and then heating these fibers to a temperature of at least 100 ° C .

2. The method according to claim 1, wherein the fibers to be lightened or dyed are polyester fibers, polyacrylonitrile fibers, polyamide fibers, polyurethane fibers, polypropylene fibers, viscose fibers and mixtures of these fibers with one another.

3. Lightened or dyed fibers with a lightened or dyed area on the outside, and a barely or barely lightened area in the core, obtainable by the process according to claim 1 or 2.