KR101076621B1 - - Process for incorporation of UV-luminescent compounds in polymeric materials - Google Patents

Abstract

The present invention is characterized in that the fibers are treated with a composition comprising (a) at least one luminescent lanthanide chelate containing three organic anionic ligands having at least one UV absorbing group, and (b) at least one solvent. A method of making luminescent textile fibers.

Luminescent Lanthanide Chelate, UV Absorbing Group, Luminescent Textile Fiber, Anti-Counterfeit, Luminescent Plastic

Description

Process for incorporation of UV-luminescent compounds in polymeric materials

The present invention relates to a process for the preparation of UV luminescent polymer materials and the use thereof.

There is a need to provide textiles with converting effects, which can act as security marks visible only under UV irradiation, which can act as special effects or as decoration.

Accordingly, it is an object of the present invention to include all materials which are invisible to the naked eye, but which exhibit a strong luminescence under UV exposure, including all conventional materials of polymeric materials including textiles such as woolen fabrics, silk fabrics, cellulose materials, natural and synthetic fibers. To provide dyeing compositions that can be used for bulk dyeing of polymeric materials, including those used in dyeing applications as well as those used in textile and plastics applications.

The present invention,

(a) one or more luminescent lanthanide chelates containing three or four organic anionic ligands having one or more UV absorbing groups, and

(b) treating the fibers with a composition comprising at least one solvent.

Preferably, component (a) is a compound of formula (I).

_{^{L m -Ln 3+ (Ch -)}} n

In Formula I,

Ln represents a lanthanide,

Ch ⁻ is a negatively charged ligand containing at least one UV absorbing double bond,

n is 3 or 4, m is a number from 0 to 4,

when n is 3 m is a number from 0 to 4 and L is a neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand, or when n is 4 m is 1 And L is a single charge cation.

More preferably, component (a) is a compound of formula II, III or IV.

In Chemical Formulas II, III, and IV,

Ln represents a lanthanide,

n represents 3 or 4, m represents a number from 0 to 4,

when n is 3 m is 0 to 4 and L is a neutral monovalent or polyvalent nitrogen-, oxygen- or sulfur-containing ligand, or when n is 4 m is 1 and L is a single charge cation ,

R ₂ is hydrogen or C ₁ -C ₆ alkyl,

R ₁ and R ₃ , independently of one another, are hydrogen, C ₁ -C ₆ alkyl, CF ₃ , C ₅ -C ₂₄ aryl or C ₄ -C ₂₄ heteroaryl.

Compounds of formula (I), (II), (III) or (IV) are basically any neutral monovalent or polyvalent nitrogen-, oxygen- or sulfur-containing ligands, such as unsubstituted or substituted pyridine, pyrazine, pyridine, quinoline , Aniline, bipyridine, phenanthroline, terpyridine, imidazole, benzimidazole, bisimidazole, bisbenzimidazole, pyrimidine, bipyrimidine, naphthyridine, alkylamine, dialkylamine, triacylamine , Alkylene polyamines, dioxane, dimaticsulfoxide, dimethylformamide, phosphine-oxide derivatives (trialkyl or triaryl), triazine, bistriazine, oxazole, bisoxazole, oxazoline, bisoxa Sleepy and substituted derivatives thereof, and all relevant (poly) N-oxide derivatives of the ligands mentioned above.

Particularly preferred compounds are compounds of formula (I), (II), (III) or (IV) wherein n is 3 and L is a nitrogen-containing ligand.

Since L can be, for example, a polychelate ligand such as 4,4'-bipyridyl, the compounds of formulas (I), (II), (III) and (IV) are multimetallic chelates, for example bivalent ligands. Compounds of formula (XIII) and (XIV) containing two M ^III- (diketone) ₃ or M ^III- (carboxylate) ₃ units linked via:

When n is 4, L is a single charge cation, essentially any metal cation (e.g. Li ⁺ , K ⁺ , Na ⁺ ), unsubstituted or substituted ammonium (e.g. NH ₄ ⁺ , polyalkylammonium) Or any monovalent or polyvalent ligand, protonated or alkylated as described above.

Preferred positively charged ligands are piperidinium, ammonium, alkylammonium, dialkylammonium and especially trialkylammonium.

Triethylammonium is particularly preferred.

Particularly preferred compounds are those of the formula I, II, III or IV, wherein L is a compound of formula V to XII or a cation of formula HN ⁺ (R ₇ ) ₃ :

In Chemical Formulas V to XII,

R ₄ , R ₅ and R ₆ independently of one another are hydrogen, halogen, C ₁ -C ₆ alkyl, C ₅ -C ₂₄ aryl, C ₆ -C ₂₄ aralkyl, C ₁ -C ₆ alkoxy, amino, dialkylamino Or a cyclic amino group,

R ₇ is hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₂₄ aryl, C ₆ -C ₂₄ aralkyl or vinyl.

Alkyl groups as substituents R ₁ to R ₇ may be straight or branched chain. Examples that may be mentioned are methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl and isohexyl There is this.

The alkoxy group as substituents R ₄ to R ₆ may be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.

Examples of C ₅ -C ₂₄ aryl groups include phenyl, tolyl, mesityl, isityl, diphenyl, Naphthyl and anthryl. Phenyl is preferred.

The heteroaryl group preferably contains 4 or 5 C atoms and 1 or 2 heteroatoms selected from O, S and N. Examples are pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, furinyl or cynolyl.

Aralkyl groups as substituents R ₄ to R ₇ are, for example, benzyl, 2-phenylethyl, tolylmethyl, mesitylmethyl and 4-chlorophenylmethyl.

Suitable dialkylamino groups are, for example, diethylamino, diisopropylamino, di-n-propylamino, N-methyl-N-ethylamino, and especially dimethylamino or pyrrolidino.

Suitable cyclic amino groups are pyrrolidino and piperidino.

The halogen atom as substituents R ₄ to R ₆ is preferably fluorine, chlorine or bromine, in particular chlorine.

Preferred compositions according to the invention are those in which L is a compound of the formula V, VI, VII, VIII, IX, X, XI or XII wherein R ₄ , R ₅ and R ₆ are hydrogen, methyl, amino, pyrrolidino or Dimethylamino) or a compound of formula (II) wherein L is a cation of formula HN ⁺ (R ₇ ) ₃ , wherein R ₇ is C ₁ -C ₆ alkyl.

Preferred component (a) is a compound of formula (I), (II), (III) or (IV) wherein Ln is Eu, Tb, Dy, Sm or Nd.

Preference is also given to compounds of the formulas (II) and (III) in which R ₁ and R ₃ are methyl, t-butyl, n-pentyl or phenyl.

R ₂ in formula (II) is preferably hydrogen.

Particularly preferred compounds as component (a) are those of the formulas XIII to LII:

XIII

Formula XIV

Some preferred derivatives of the structures of Forms II and III, derived from the preferred structures of Form I presented above, are summarized in the table below:

DMAP: 4-dimethylaminopyridine

Another suitable lanthanide chelate is,

Pyridine, aminopyridine, pyrrolidinopyridine, methylpyridine, methoxypyridine, pyridine-N-oxide, bipyridine, phenanthroline, imidazole, or any other derived or similar N, O or Contains S-containing monovalent or polyvalent ligands,

Instead of Et ₃ NH ⁺ , it may contain piperidinium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, pyridinium, or any other similar N-containing protonated species.

For certain applications, it may be advisable to use combinations of different lanthanide compounds such as Eu and Tb together. This mixture increases the security of the hidden coloring, complicates the security level, and doubles the cryptographic possibilities.

Compounds of formulas (I), (II), (III) and (IV ) are known or known, for example, in International Patent Application Publication WO 96/20942 and in CR Hurt et al., Nature 212 , 179-180 (1966). It can be prepared according to the method described. For example, ligands such as acetylacetone, benzoylacetone, dibenzoylmethane, dipivaloylmethane, salicylic acid, valeric acid or caproic acid are reacted with rare earth metal halides, for example, lanthanide trichloride, under appropriate conditions, Prepare metal chelates. Further reaction with monovalent or polyvalent nitrogen-, oxygen- or sulfur-containing ligands L produces rare earth metal chelates of formulas (I), (II), (III) and (IV).

Luminescent lanthanide chelates can be applied as powders, solutions or dispersions.

Thus, component (b) can be water, an organic solvent, a mixture of two or more organic solvents, or a mixture of water and one or more organic solvents.

Preferably, component (b) may be water, one or more water-miscible organic solvents, or a mixture of water and one or more water-miscible organic solvents.

Suitable organic solvents include alcohols, glycols, ether alcohols, sulfoxides, amides, amines, heterocyclic solvents, ketones, ethers, esters, nitriles, and aliphatic, cycloaliphatic and aromatic hydrocarbons.

Examples of suitable organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol monoethyl ether, polyethylene Glycol dimethyl ether, ethoxybutanol, 2-butoxyethanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetone, 2-buta Paddy, diethylether, di-n-propylether, tetrahydrofuran (THF), ethyl acetate, ethyl propionate, acetonitrile, pyridine, n-pentane, n-hexane, cyclohexane, benzene and toluene.

Water-miscible organic solvents are preferably aliphatic alcohols, etheralcohols, glycols, aliphatic ketones, carboxylic esters, carboxylic acid amides, aliphatic nitriles, aliphatic polyethers or aliphatic sulfoxides.

Particularly preferred water-miscible organic solvents are ethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile, polyethylene glycol dimethyl ether and dimethyl sulfoxide (DMSO).

The composition according to the invention may, in addition to components (a) and (b), comprise (c) one or more colorants.

Suitable colorants are well known pigments and dyes comprising mixtures of different pigments and dyes.

In the compositions according to the invention, the amounts of components (a) and (b), optionally component (c) and / or additional component (d), can vary within wide limits.

For mass-dyeing processes, the composition according to the invention consists of component (a). Optionally, additional components (c) and / or (d) are added together with component (a) to simultaneously impart auxiliary properties to the polymeric material, in addition to UV-luminescent properties.

In the dyeing process, preferred compositions comprise 0.01 to 20.0% by weight, more preferably 0.05 to 10% by weight, in particular 0.1 to 5.0% by weight, based on the total amount of components (a) + (b) ) And 80.0 to 99.99% by weight, more preferably 90.0 to 99.95% by weight, in particular 95.0 to 99.9% by weight of component (b).

The amount of component (c) depends on the type of substrate and the particular pigment or dye. Based on the weight of the fibers, the advantageous amount of colorant is generally from 0.01 to 15% by weight, in particular from 0.1 to 10% by weight.

Additional components (d) which may be present in the composition according to the invention are, for example, optical brighteners, biocides, bactericides, fungicides, insecticides and fragrances.

Compositions containing one or more lanthanide chelates may be prepared by any suitable method known to those skilled in the art. For example, the components of the composition can be formulated or mixed in a suitable mixer or mixer.

The compositions according to the invention are useful for impregnating the natural, artificial and especially synthetic hydrophobic materials produced, in particular textile materials.

Textile materials consisting of blended fabrics comprising such prepared natural polymer or synthetic hydrophobic fiber materials can likewise be impregnated with the formulations according to the invention.

Useful manufactured natural polymeric textile materials are especially wool, cotton, silk, cellulose acetate and cellulose triacetate.

Synthetic hydrophobic textile materials include, in particular, linear aromatic polyesters such as terephthalic acid and glycols, in particular polyesters formed from ethylene glycol, or condensation products of terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane; Polycarbonates such as those formed from α, α-dimethyl-4,4′-dihydroxydiphenylmethane and phosgene; Or fibers based on polyvinyl chloride or polyamide.

The formulations according to the invention are applied to textile materials according to known dyeing processes. For example, the polyester fibers are dyed with an aqueous dispersion in the presence of a conventional anionic or nonionic dispersant, with or without a conventional carrier, at a temperature of 80 to 140 ° C., preferably 120 to 135 ° C. . Cellulose acetate is preferably dyed at 60-85 ° C. and cellulose triacetate is dyed at 115 ° C. or lower.

The formulations used according to the invention are useful for dyeing and printing by thermosol processing, dyeing processing and continuous processing. Dyeing is preferred. The solution ratio depends on the device, substrate and preparation. However, the solution ratio may be selected within a wide range, for example 4: 1 to 100: 1, but is preferably 6: 1 to 25: 1.

The textile materials mentioned may be present in various processing forms, for example as fibers, yarns or webs, or as woven or loop-forming knitted fabrics.

The luminescent lanthanide chelates of the present invention are also useful for mass-dyeing plastics.

Accordingly, the present invention also provides a method for producing a luminescent plastic, characterized in that the plastic material is extruded in the presence of 0.01 to 10.0% by weight of the compound of formula (I), (II), (III) or (IV) based on the amount of the plastic material. It is about.

Plastics useful for bulk dyeing are, for example, dyeable high molecular weight organic materials (polymers) having a dielectric constant of 2.5 or more, in particular polyester, polycarbonate (PC), polystyrene (PS), polypropylene (PP), polymethyl Methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene / acrylonitrile (SAN) or acrylonitrile / butadiene / styrene (ABS). Preferred are polyesters and polyamides. Particularly preferred are polyesters obtainable by polycondensation of terephthalic acid and glycols, in particular ethylene glycol, or condensation products of terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, for example polyethylene terephthalate (PET) or Polybutylene terephthalate (PBTP); Polycarbonates such as polycarbonates formed from α, α-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; Polymers based on polyvinyl chloride or polyamide, for example nylon 6 or nylon 6.6, polystyrene (PS) or polypropylene (PP).

Very particular preference is given to linear aromatic polyesters such as terephthalic acid and glycols, especially those formed from ethylene glycol, or condensation products of terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, polymethyl methacrylate ( PMMA), polypropylene (PP) or polystyrene (PS) based plastics.

The plastics can, for example, be mixed with the luminescent lanthanide chelate according to component (a) into the substrate using a roller mill or mixing or grinding device, thereby allowing the lanthanide chelate to be dissolved or finely dispersed in the plastic. Dyed. The plastic mixed with the dye is then processed in a conventional manner, for example by calendering, pressing, extruding, spread coating, spinning, casting or injection molding, whereby the dyed material is used to form its final shape. Acquire. In addition, the mixing of the components may be effected immediately prior to the actual processing step, for example by simultaneously mixing the solids such as powdered lanthanide chelates and granulated or powdered plastics and optionally further materials, for example additives, immediately before processing. This is achieved by metering continuously into the inlet of the extruder that takes place. In general, however, it is preferable to premix lanthanide chelates in the plastic, since a more uniformly impregnated substrate can be obtained.

In addition, the present invention relates to luminescent textile fibers and luminescent plastics produced by the above process.

Through the present invention, colorless or colored hidden markings can be incorporated into various colorless, white, pale, or dark colored substrates so that they appear under UV exposure.

The claimed method is particularly useful for the manufacture of security fibers or security threads that can be applied to credit documents or other materials. Secure fibers are incorporated into credit documents or other materials for the purpose of ensuring protection against identification, authentication, forgery, imitation or tampering. A secure seal is a continuous seal or strip of film introduced into a credit document for the same purpose as a secure fiber.

The expression "credit document" means not only paper such as banknotes, checks, stocks, stamps, official documents, identity documents, passports, records books, bills, medicine slips, receipts, newsletters and books, but also credit cards, payment cards, and access books. Card, and similar documents requiring a high level of security.

The production of security fibers or security yarns can be carried out by known methods, for example by the methods described in US Pat. Nos. 4,655,788, 5,759,349 and 6,045,656, EP-A 185 396 and EP-A 1 013 824. have.

The incorporation of lanthanide chelate compounds can be carried out by conventional dyeing or printing processes.

Fibers suitable for the claimed method can be obtained from wood or plant pulp, cellulose pulp, cotton fabrics, flax fibers or synthetic fibers.

Preferably, paper fibers or synthetic fibers are used.

In a particularly preferred aspect, the method according to claim 1 is used for the production of anti-counterfeiting documents, cards, checks or banknotes.

The composition according to the present invention is distinguished from similar compositions of the prior art by the remarkable amount of luminescence, long lasting luminescence and high luminescence intensity.

The following examples illustrate the invention.

Ink Composition A:

Concentrate of Compound XVII in 1,2-propylene glycol

1 g of compound VIII is heated at 100 ° C. for 1 hour to dissolve in 99 g of 1,2-propylene glycol. A stable ink composition is produced which cools the clear yellow solution and shows strong red light emission under UV light after filtration (purification). Such concentrates may also be used in conventional or advanced technology (ink-jet) printing formulations of solvent or aqueous systems for paper, textiles, leather, wood, plastics or other suitable substrates.

Example 1

Impregnation of cellulose bobbins (0.75 kg cotton yarn 40 tex) is performed at 35 ° C. in a Calebault de Blicquy (3 min cycle) in a 1 to 10 solution ratio. The solution contains 4.5% of the compound of formula XVII in 2-butoxy-ethanol:

Formula XVII

After treatment, the bobbins were centrifuged and air-dried, and strong red-orange fluorescence was observed under UV light.

Example 2

Impregnation of silk (10 g) is carried out at 25 ° C. for 10 to 60 minutes, in the same solution and to the textile material as described in Example 1. After treatment, the silks were centrifuged and air-dried to show strong red-orange fluorescence under UV light.

Example 3

Impregnation of a patchwork fabric (10 g) containing several distinct bands of synthetic, artificial, natural (vegetable and animal) fibers was carried out at 25 ° C., at a solution ratio for the same solution and textile material as described in Example 1 Run for 10 to 60 minutes. After treatment, the patchwork was centrifuged and air-dried to show strong red-orange fluorescence under UV light in most fibers.

The same results are obtained from similar processes using different lanthanide complexes (eg terbium, dysprosium, samarium, neodymium) exhibiting different emission wavelengths under UV irradiation.

Example 4

High Temperature Dyeing (HTD) of Polyester (PES) Filament (135 ° C, 60 minutes)

PES filaments (10 g) are introduced into a 250 mL leak-proof bottle containing 200 ml of dye bath (i.e. bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XVII dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

0.6 g / l Univadin DP (Ciba Specialty Chemicals)

2.5 g / l Cibatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The PES filaments thus treated exhibit strong red-orange fluorescence under 365 nm light.

Example 5

High Temperature Dyeing (HTD) of Velvet PES Fabrics (135 ° C, 60 minutes)

Velvet PES fabric (10 g) is introduced into a leak-proof 250 mL bottle containing 200 ml of dye bath (ie, bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XVII dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The PES filaments thus treated exhibit strong red-orange fluorescence under 365 nm light.

Example 6

High Temperature Dyeing (HTD) of Velvet PES Fabrics (135 ° C, 60 minutes)

Velvet PES fabric (10 g) is introduced into a leak-proof 250 mL bottle containing 200 ml of dye bath (ie, bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XV dissolved in NMP (5-30ml)

XV

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The velvet PES fabrics thus treated exhibit strong green fluorescence under 254 nm light.

Example 7

High Temperature Dyeing (HTD) of Polyamide (PA) Tricot (135 ° C., 60 minutes)

PA trico (10 g) is introduced into a 250 mL leak-proof bottle containing 200 ml of dye bath (i.e. bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XVII dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The PA tricots thus treated show strong red-orange fluorescence under 365 nm light.

Example 8

High Temperature Dyeing (HTD) of PA Tricot (135 ° C, 60 minutes)

White PA Tricot (10 g) is introduced into a 250 mL leak-proof bottle containing 200 ml of dye bath (i.e. bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XV dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The PA Tricot thus treated is white and shows green fluorescence under light of 254 nm.

Example 9

High temperature dyeing (HTD) of clear colorless PA yarn (135 ° C, 60 minutes)

A clear, colorless PA seal (10 g) is introduced into a 250 mL leak-proof bottle containing 200 ml of dye bath (i.e. bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XVII dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The transparent PES yarn thus treated showed strong red-orange fluorescence under 365 nm light.

Example 10

Incorporation of the compound of formula XVII into polyamide (PA) by mass-staining method

In the presence of 2% of the lanthanide complex of formula XII, Ultramidd B3K extruded at 260 ° C. for 2 minutes shows red-orange color under light of 365 nm.

Example 11

Incorporation of the compound of formula XVII into polystyrene (PS) by mass-staining method

Polystyrol H165 extruded at 300 ° C. for 5 minutes in the presence of 2% lanthanide complex of formula XVII shows red-orange color under light of 365 nm.

Example 12

Incorporation of the compound of formula XVII into polypropylene (PP) by mass-staining method

A homogenized mixture of polypropylene granules (200 g) and compound XVII (2 g) is introduced into a fusion chamber (200 ° C.) of a 3 mm cable extruder. After cooling in the water bath, the rigid cable thus obtained is again cut into granules and introduced again into the fusing chamber (230 ° C.) of the filament extruder. The thin polypropylene yarn (8 dtex) of the transparent multifilament thus obtained shows strong red-orange fluorescence when excited at 365 nm.

Example 13

Incorporation of the compound of formula XVII into polypropylene (PP) by mass-staining method

Similar processes and the resulting fluorescent properties are obtained when using titanium dioxide simultaneously with compound XVII.

Example 14

Incorporation of the compound of formula XVII into poly (methylmethacrylate) (PMMA) by mass-staining method

In the presence of 2% lanthanide complex of formula XVII, Plexiglas 6N extruded at 260 ° C. for 5 minutes shows red-orange fluorescence under light of 365 nm.

Example 15

Incorporation of the compound of formula XVII into acrylonitrile / butadiene / styrene-copolymer (ABS) by mass-staining method

In the presence of 2% lanthanide complex of formula XVII, Terluran 877M extruded at 220 ° C. for 5 minutes exhibits red-orange fluorescence under light of 365 nm.

Example 16

High Temperature Dyeing (HTD) of Colored PES Fine Thread (135 ° C, 60 minutes)

Thin cyan PES yarn pre-mass-dyed with a mixture of Irgalite Blue GLGP ( CI Pigment Blue 15: 3 ), titanium dioxide ( CI Pigment White 6 ) and carbon black ( CI Pigment Black 7 ) (10 g) Is introduced into a 250 mL bottle that is leak-proof containing 200 ml of dye bath (ie, a bath ratio of 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XV dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The thin cyan PES yarn thus treated is cyan and exhibits strong green fluorescence under 254 nm light, but does not fluoresce under 365 nm light.

Example 17

High Temperature Dyeing (HTD) of Colored PES Fine Thread (135 ° C, 60 minutes)

A 200 ml dyeing bath (i.e., bath ratio of 1 to 20) was prepared from 200 ml of a thin black PES yarn (10 g) pre-mass-dyed with a pigment mixture containing titanium dioxide ( CI Pigment White 6 ) and carbon black ( CI Pigment Black 7 ). ) Into a 250 mL leak-proof bottle.

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XV dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The thin black PES yarn thus treated is black and exhibits strong green fluorescence under 254 nm light, but does not fluoresce under 365 nm light.

Example 18

High Temperature Dyeing (HTD) of Colored PES Fine Thread (135 ° C, 60 minutes)

Leak-proof, containing 200 ml of dye bath (i.e. bath ratio 1 to 20), a thin yellow PES yarn (10 g) pre-mass-dyed with Filester Yellow RNB ( CI Pigment Yellow 147 ) Into a 250 mL bottle.

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XV dissolved in NMP (5-30ml)

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The thin yellow PES yarn thus treated is yellow and exhibits a strong green-yellow fluorescence under 254 nm light, but does not fluoresce under 365 nm light.

Example 19

High Temperature Dyeing (HTD) of PES Filament (135 ° C, 60 minutes)

PES filaments (10 g) are introduced into a 250 mL leak-proof bottle containing 200 ml of dye bath (i.e. bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XXI dissolved in NMP (5-30ml)

Formula XXI

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The PES filaments thus treated exhibit strong red-orange fluorescence under 365 nm light.

Example 20

High Temperature Dyeing (HTD) of PES Filament (135 ° C, 60 minutes)

The white PES filament (10 g) is introduced into a 250 mL leak-proof bottle containing 200 ml of dye bath (i.e. bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

NMP suspension (5-30 ml) containing 2% lanthanide complex of formula XX

Formula XX

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The white PES filaments thus treated are white and exhibit pink-red fluorescence under 254 nm light, but do not fluoresce under 365 nm light.

Example 21

High Temperature Dyeing (HTD) of PES Filament (135 ° C, 60 minutes)

The white PES filament (10 g) is introduced into a 250 mL leak-proof bottle containing 200 ml of dye bath (i.e. bath ratio 1 to 20).

The dye bath is prepared as a mixture of the following two solutions:

Solvent-based solution containing 3-5% lanthanide complex of formula XXII dissolved in NMP (5-30ml)

Formula XXII

○ aqueous solution containing the following substances, pH = 4.5 (195-170 ml)

Unibadine DP (Ciba Specialty Chemicals) of 0.6 g / l

2.5 g / l Sivatex AB 45 (Ciba Specialty Chemicals)

■ 0.4 g / l sodium bicarbonate.

The bottle is placed in a rotary hot dye autoclave and the bath temperature starts at 70 ° C. The temperature is then raised to 135 ° C. over 30 minutes and kept stable for an additional hour. Finally, the treatment temperature is lowered to 40 ° C. over 15 minutes, after which the yarn is taken out of the bottle, rinsed with hot water (35 ° C.) for 5 minutes, rotary dried, and finally with hot air (90-105 ° C.) To dry. The white PES filament treated in this way is white and exhibits green fluorescence under 254 nm light, but does not fluoresce under 365 nm light.

Example 22

High Temperature Dyeing (HTD) of PES (135 ° C, 60 minutes)

All of the above experiments of high temperature dyeing are also achieved by applying UV fluorescent lanthanide chelates instead of disperse dyes, by means of a preparation method similar to that of disperse dyes, without using NMP.

Example 23

Transcription printing with UV fluorescent lanthanide chelates is performed using a transcription printing formulation containing one or more UV fluorescent lanthanide chelates. These formulations are prepared analogously to conventional transfer printing formulations using one or more lanthanide chelates instead of disperse dyes, or one or more lanthanide chelates in addition to the disperse dye (s).

Example 24

Fabrication of Multi-Component Security Seals

The polymer mixture (e.g. copolymerized polyamide Akulon ^R , Akzoplastiks) is dispensed into three extruders and the granules are dissolved. The lysate, known as the external component of the yarn, is mixed with 3% by weight of the compound of formula XVII, respectively, so that it is uniformly dissolved in the polyamide lysate. After extrusion of the multi-component yarns, a security yarn is obtained in which the edge strips fluoresce under UV light but the central strip does not fluoresce any fluorescence. By co-extrusion of the lanthanide chelate (s) with one or more dyes or pigments, a similar fluorescent colored yarn is obtained under UV light.

Example 25

Fabrication of Multi-Component Security Seals

As described in Example 24, security seals are prepared by extruding a polyamide lysate containing 3% by weight of a 1: 1 mixture of a compound of formula XVII and a compound of formula XV. Upon irradiation with different wavelengths of UV light, red and / or green fluorescence is observed.

Claims (20)

(a) a compound of Formula II, III or IV and (b) treating the fibers with a composition comprising at least one solvent. Formula II

Formula III

Formula IV

In Chemical Formulas II, III, and IV, Ln represents a lanthanide, n represents 3, m represents a number from 0 to 4, L is a neutral monovalent or polyvalent nitrogen-, oxygen- or sulfur-containing ligand, R ₂ is hydrogen or C ₁ -C ₆ alkyl, R ₁ and R ₃ , independently of one another, are hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₂₄ aryl or C ₄ -C ₂₄ heteroaryl. The method of claim 1 wherein said composition further comprises (c) at least one colorant. A method for producing a luminescent plastic, characterized in that the plastic material is extruded in the presence of 0.01 to 10.0% by weight, based on the amount of polymeric material, in the presence of the compound of formula II or III. Luminescent textile fibers made by the method according to claim 1. Luminescent plastics produced by the process according to claim 3. The method of claim 1 for producing an anti-counterfeiting document, card, check or banknote. delete delete delete delete delete delete delete delete delete delete delete delete delete delete