EP2859145A2

EP2859145A2 - Textile auxiliary agent and textile product finished therewith

Info

Publication number: EP2859145A2
Application number: EP13729627.3A
Authority: EP
Inventors: Tanja JAICH; Harald Lutz; Holger Danielec
Original assignee: Schoeller Technologies AG; CHT R Beitlich GmbH
Current assignee: Schoeller Technologies AG; CHT Germany GmbH
Priority date: 2012-06-06
Filing date: 2013-06-04
Publication date: 2015-04-15
Anticipated expiration: 2033-06-04
Also published as: DE102012209598A1; WO2013182568A2; WO2013182568A3; EP2859145B1

Abstract

The invention relates to a textile auxiliary agent which produces a local heating effect by absorbing the energy of electromagnetic radiation and/or by reducing the energy output, on textile surfaces, fabrics, tissues, nonwovens and wovens or products produced therefrom.

Description

Textile auxiliaries and thus refined textile product

The present invention describes a textile auxiliary which achieves a locally warming effect on energy-absorbing surfaces of electromagnetic radiation and / or on reduced energy output on textile surfaces, woven fabrics, laid fabrics, knitted fabrics, nonwovens and knitted fabrics or products made therefrom.

In the past, clothing textiles were provided with thicker lining material, additional fabric layers, heavier or denser woven textiles for better thermal insulation. This is impractical, since additional material or thicker and heavier substances increase the volume and weight of the clothing and therefore wear comfort and mobility of the wearer are impaired.

By using IR-absorbing and / or -reflective layers of different materials such as aluminum or carbon, the problem has been solved in JP 2005212471.

However, this approach is technically complex, costly and not compatible with colored, especially light or white, textiles. Another approach is to influence the amount of heat in the form of radiation emitted by the body to be heated by the clothing. By gas deposition processes in the patent application JP 2005290585 radiation-absorbing layers are applied to textiles. This problem solution is very costly and technically complex.

EP 1 792 724 A2 describes two-sided coating with a tourmaline tape in order to reduce the emission of material from the body of the wearer wearing the clothing. This approach requires a special apparatus described in the patent and such textiles have undesirable color changes and haptic changes.

The application of thermal radiation by the use of dark dyes describes the patent application JP 2009062652. EP 1 847 635 A1 describes the use of IR-reflecting pigments based on activated tungsten oxides. Organic bisiminium compounds are used in Japanese Patent Application JP 2009203596 to produce IR absorbing textiles. However, these approaches are unsuitable for producing colorless or light-colored textiles. In DE 39 21 249 A1, IR-absorbing dyes based on conductive organic polymers are used on textiles in order to reduce the emitting heat radiation and thus the detectability by night vision devices.

Benzoxazoline-based UV absorbers are incorporated with transparent conductive oxides in polyester fibers by melt-spinning processes. Thus the authors achieve an improvement of the Thermal insulation. Japanese patent JP 2004149931 describes the use of zirconium carbide, titanium oxide or special metal complexes as IR radiation absorbing compounds for the use of underwear.

As transparent conductive oxides, binary or ternary oxides of some transition metals are mentioned. The preparations and their applications also on textiles have long been known. For example, WO 01/25367 A1 describes the preparation of such oxides by the hydrothermal route and the use thereof to produce textiles with sensor properties or antistatic effects. Already in EP 0 341 554 A1, large quantities of such oxides are added to synthetic fibers in a masterbatch application in order to produce conductive textiles. To achieve angle-dependent color effects of textiles, TW 201113410 uses indium tin oxide in combination with titanium oxide layers. In none of these writings is the heat retention of textbooks corresponding to processed textiles. Such ternary oxides have a graying or generally a clearly color-changing effect as a textile auxiliaries.

Methods for lowering remission or reflection are used primarily for camouflage purposes in the military sector. Above all, the radiation ranges of the infrared light are influenced. For example, DE 10 258 014 A1 describes a method for introducing glass fibers coated on one side with aluminum powder in heat-treated blankets, in order to enable visible-optical camouflage by reducing the emitted thermal radiation. The reflective layers are directed towards the heat source.

Frequently, methods for coating and / or vapor deposition with metallic layers on textile substrates or in textiles described. An example based on an aluminum coating is shown in WO 2004/020931 AI. These processes have the disadvantage that they greatly affect the textile, resulting in haptic, color and comfort losses.

Metallic and polymeric nanoparticles for the modification of reflection and / or remission are described in WO 2010/120531 Al.

Another commonly described method for influencing the reflection and / or remission is the selection of suitable colorants. Reduction of the remission of textiles is reported in, for example, RU 2196855 and PL 202000. By the method described therein, however, can only produce colored textiles.

The influence especially black textiles is described in WO 2009/118419 AI. By selecting the colorants, an increase in near-infrared reflection is reported, thereby achieving a reduction in the amount of heat absorbed by textiles.

DE 10 2009 006 832 A1 describes a liquid or semi-solid formulation of spectrally selective particles for coating flexible bodies. The coating is characterized by having a significantly lower thermal emissivity at room temperature than the uncoated body, while maintaining the body's texture / texture and flexibility. In addition, the coatings can be given a virtually arbitrary color impression, while maintaining a lowered emissivity. EP 1 321 291 A1 and EP 1 437 438 A1 describe textile auxiliaries for IR absorption and / or reflection and the use of the semiconductors indium tin oxide and antimony tin oxide.

DE 39 21 249 A1 describes IR-absorbent textiles which are equipped against detection by indulgence devices with IR-absorbing compounds which are conjugated organic polymers.

WO 2008/004993 A2 describes layers with absorptions in the near infrared range as well as corresponding articles containing these layers. This should not change the visual impression of the entire article.

All of the aforementioned approaches have in common that the properties such as color, comfort or handle of the textile are adversely affected, the solutions are technically complex or costly or that no heat retention and Remissionsverbesserung is achieved.

Surprisingly, it has been found that by using suitable semiconductors and in particular by combinations thereof non-color-modifying electromagnetic radiation absorbing layers can be applied permanently and wash-permanently on textiles, whereby textiles under IR or solar radiation absorb an increased amount of heat and / or deliver a reduced amount of heat. It has been found, particularly surprisingly, that the described effect can be synergistically enhanced by the selection of suitable binder polymers. The invention in a first embodiment, a textile auxiliary for IR absorption and / or reflection of textiles, containing

(a) at least one semiconductor,

(b) one or more binder polymers from the group of polyurethanes, polyacrylates, styrene-butadienes, silicones, siloxanes, sol gels, polyvinyl chloride, ethylvinyl acetate, epoxy or polyester resins,

(C) surfactants selected from the group of anionic, cationic or nonionic surfactants and

(d) solvent and / or further dispersing aids.

The present invention combines the simplicity of already existing textile-technological processes such as equipment by pad-forced application, coating by means of pastes or foams, spray application, printing, dipping and exhausting process and single filament application on Galette or in the dip bath with an effect of increased heat energy absorption or reduced heat emission (-. loss) of such finished textiles by selecting suitable compounds. By the practice of this invention, textile parameters such as hand and tear are not adversely affected. In particular, the color of a textile is not adversely affected. Thus, white or colorless textiles can be refined with this invention.

By applying the invention, such a finished textile under the influence of electromagnetic radiation heats significantly more than a corresponding comparison pattern of the same parameters (eg material composition, color, weight, thickness, structure and weaving). At the same time this can be a reduction of the remission Electromagnetic radiation and / or increase the absorption thereof.

According to the invention, the use of suitable semiconductors together with other components solves the technical problem. From the group of semiconductors, inorganic, including elemental and oxidic as well as organic semiconductors are used. The first group a) includes the compounds of the A ^m B ^v type semiconductor (see AF Holleman, E. Wiberg, Lehrbuch der anorganischen Chemie, 101st ed., De Gruyter, Berlin, pp. 1098-1100).

Suitable elementary semiconductors of group b) are suitable modifications of tin, indium, carbon, silicon and germanium.

In the third group c) fall organic conductive polymers.

The group d) of the oxide semiconductor includes conductive transparent oxides.

The A ^m B ^v -Halbleiter type of the group in the context of this invention comprises the compounds AB of the elements A, wherein A for aluminum, gallium, indium, thallium, germanium, tin, lead and B for nitrogen, phosphorus, arsenic, antimony and Bismuth in any stoichiometric ratios. Particularly preferred within the meaning of the invention are the binary pentel compounds of aluminum, in particular aluminum nitride, since they are generally distinguished by high chemical inertness.

For the purposes of the present invention, organic conductive polymers such as polypyrrole, polyaniline, polyparaphenylene, polythiophene, poly (4,4-dioctylcyclopentadithiophene), poly (3,4-ethylenedioxythiophene) or Poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate) as a semiconductor alone or in combination with other suitable conductive polymers solve the technical problem.

Suitable oxides from group d) are transparent conductive oxides of the type A _n B _m O _x , where A can be fluorine, indium, magnesium, aluminum, chromium, zinc or antimony and B is zinc, titanium or tin, and n is a number between 0 and 1 and m = ln, where x takes the required number for the stoichiometric saturation of the metals. This group includes, for example, fluorine doped tin oxide, indium tin oxide, antimony tin oxide, aluminum zinc oxide, magnesium zinc oxide, chromium titanium oxide. The transparent conductive oxides can particularly preferably be used in combination with suitable polymers in the preparation.

Surprisingly, it has been found that a synergistic effect is found by combining the semiconductors. In particular, the semiconductors are selected from at least one of the semiconductors of groups a), b) and c) and furthermore at least one semiconductor from group d), or mixtures of at least two semiconductors selected from groups a), b) and c), in particular at least one from group a) and at least one from group c) or at least two semiconductors from group d).

Furthermore, certain, infrared radiation-absorbing dyes may optionally be additionally contained in small amounts in order to increase the effect of heat absorption. Such infrared radiation absorbing materials according to the invention can be either organic or inorganic as defined above. In general, infrared radiation-absorbing materials in the sense of the invention are materials which have a wavelength range of 700 to 35,000 nm at at least two of the wavelengths 1000 nm, 1500 nm, 2000 nm and 3500 nm have a molar extinction coefficient of at least 1.5 l mol.cm ^-1 . Particularly preferably, the infrared radiation absorbing material has an absorption maximum in a range from 900 to In particular, a material selected from the group consisting of phthalocyanines, naphthalocyanines, anthraquinones, cyanine compounds, squalylium compounds, thiolnickel oxides, is used as organic infrared radiation absorbing material.

Complex compounds, triallylmethanes, naphthoquinones, anthraquinones and amine compounds such as N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-phenylenediaminium perchlorate, Phenylenedi- aminium chlorate, Phenylenediaminium hexafluoroantimonat, Phenylenediaminium fluoroborat, Phenylenediaminium fluorat and Phenylenediaminium perchlorate.

The particulate semiconductors used in this invention have a particle size (number average, d ₅ o, laser diffraction) of 1 nm to 10 μιτι, preferably less than 2 μιτι on.

According to the invention, the use of one or more of the abovementioned semiconductors from the abovementioned groups a), b), c) or d) solves the technical problem. Optionally, the effect can be synergistically enhanced by infrared-absorbing organic dyes.

Surprisingly, it has been found that through the use of said semiconductors, and in particular the said combinations thereof, the heat absorption can be increased and remission can be lowered without changing the base color of a textile material. It has been found, particularly surprisingly, that synergistic effects can be achieved by combining a plurality of semiconductors. By means of the textile auxiliaries according to the invention, elaborate dyeing tests are avoided in order to achieve a desired hue of the finished textile. In the textile industry, the subsequent process steps must not have any color-changing effects on the coloration, since these must be considered and compensated a priori. By the method thus bright or white textiles with the desired properties can be produced.

Suitable binder polymers for the semiconductors are, for example, homopolymers, copolymers or terpolymers based on polyacrylates, polyurethanes, styrene-butadienes, sol-gels, silicones, epoxide resins, polyvinyl chloride, ethylvinyl acetate, polyester resins or mixtures of these classes in the invention. Cross-linked, cross-linking or reactive systems are preferred for the purposes of the invention, particularly preferably those whose films show a glass transition state of less than 0 ° C.

Suitable starting components for the polyurethanes of the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those of the formula

Q (NCO) _n in the n = 2 to 4, and Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 5 to 10 C atoms, an aromatic hydrocarbon radical with 6 to 15, preferably 6 to 13 C atoms, or an aliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13 C atoms, for example Ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-

Hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane

1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-tri-methyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2, 6-Hexahydrotoluylendiisocyanat and any mixtures of these isomers, hexahydro-1,3- and -1,4-phenylene diisocyanate, perhydro-2,4'- and -4,4'-diphenyl-methane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 1,4-diol diisocyanate (DDI), 4,4'-stilbenediisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI)

2,4- and 2,6-toluene diisocyanate (TDI) and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate (MDI), and / or naphthylene-l, 5-diisocyanate (NDI ).

Also suitable are, for example: triphenylmethane-4,4 ', 4 "- triisocyanate, polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in GB-PS 874 430 and GB-PS 848,671 described, m- and p-Isocyanatophenylsulfonylisocyanate according to US Patent 3,454,606, perchlorinated aryl polyisocyanates, as described in US-PS 3,277,138, carbodiimide-containing polyisocyanates, as described in US-PS 3,152,162 and in DE-OS 25 04 400, 25 37 685 and 25 52 350, norbornane diisocyanates according to US Pat. No. 3,492,301, allophanate-containing polyisocyanates, as described in GB-PS 994 890, BE-PS 761 626 and NL-A 7 102 524, containing isocyanurate polyisocyanates, as described in US-PS 3,001,971, in DE-PS 10 22 789, 12 22 067 and 10 27 394 and in DE-OS 19 29 034 and 20 04 048, having urethane groups Polyisocyanates, such as they are described, for example, in Belgian Pat. No. 752,261 or in US Pat. Nos. 3,394,164 and 3,644,457, acylated polyisocyanates containing urea groups according to DE-PS 12 30 778, biuret-group-containing polyisocyanates, as described in US Pat. No. 3,124,605, US Pat. 3,201,372 and 3,124,605; and British Patent 889,050, polyisocyanates prepared by telomerization reactions, such as described in U.S. Patent No. 3,654,106, polyisocyanates containing ester groups, as described in British Patent Nos. 965,474 and 1,072,956 , in US-PS 3,567,763 and in DE-PS 12 31 688, reaction products of the above isocyanates with acetals according to DE-PS 10 72 385 and polymeric fatty acid ester-containing polyisocyanates according to US Patent 3,455,883.

It is also possible to use the isocyanate-group-containing distillation residues obtained in industrial isocyanate production, optionally dissolved in one or more of the abovementioned polyisocyanates. Furthermore, it is possible to use any mixtures of the aforementioned polyisocyanates.

Preference is given to the technically readily available polyisocyanates, for example the 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomers ("TDI"), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2 ' Diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate, as prepared by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI"), and carbodiimide groups, uretonimine groups, urethane groups,

Allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates ("modified Polyisocyanates "), in particular those modified polyisocyanates which are derived from 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate. Also suitable are naphthylene-1, 5-diisocyanate and mixtures of said polyisocyanates.

Polyacrylates in the context of the present invention are in particular prepared by solution, precipitation, emulsion or inverse emulsion polymerization.

Acrylates are preferably selected from the group consisting of 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di ( meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl di (meth) acrylate modified with caprolactam, phosphoric di (meth) acrylate modified with ethylene oxide, cyclohexyl di (meth) acrylate modified with an allyl group , Isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate modified with propionic acid, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate modified with propylene oxide, tris (acryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate modified with propionic acid, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate modified with caprolactam, (meth) acrylate esters monofunctional (M. eth) acrylate, such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Methoxypolyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate and glycidyl (meth) acrylate; difunctional (meth) acrylate, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, allyl (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, polyethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol S-di (meth) acrylate, bisphenol S-di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,3-butylene glycol di (meth) acrylate; and tri- and higher functional (meth) acrylates, such as trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene-modified trimethylolpropane tri (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl acrylate, 2 Ethylhexylcarbitol acrylate, omega-carboxypolycaprolactam monoacrylate, acryloyloxyethylic acid, acrylic acid dimer, lauryl (meth) acrylate, 2-methoxyethyl acrylate, butoxyethyl acrylate, ethoxyethoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Tetra hydrofurfuryl (meth) acrylate, N-vinyl-2-pyrrolidone, isobornyl (meth) acrylate, dicyclopentenyl acrylate, benzyl acrylate, phenyl glycidyl ether epoxy acrylate, phenoxyethyl (meth) acrylate, phenoxy (poly) ethylene glycol acrylate, nonylphenol ethoxylated acrylate, acryloyloxyethylphthalic acid, tribromophenyl acrylate, tribromophenol ethoxylated (meth) acrylate, methyl methacrylate, tribromophenyl methacrylate, methacryloxyethyl acid, methacryloyloxyethylmaleic acid, methacryloyloxyethylhexahydrophthalic acid, methacryloyloxyethyl phthalic acid, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, beta-carboxyethyl acrylate, N-methylol acrylamides, N-methoxymethyl acrylamides, N-ethoxymethyl acrylamide, Nn-butoxymethyl acrylamide , t-butyl acrylamide sulfonic acid, vinyl stearate, N-methyl acrylamide, N-dimethyl acrylamide, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl acrylamide, acryloyl morpholine, glycidyl methacrylate, n-butyl methacrylate, ethyl methacrylate, allyl methacrylate, Cetyl methacrylate, pentadecyl methacrylate, methoxypolyethylene glycol (meth) acrylate, diethylaminoethyl (meth) acrylate, methacryloyloxyethylsuccinic acid, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate monostearate, glycol diacrylate, 2-hydroxyethyl methacryloyl p phosphate, bisphenol A ethylene glycol adduct acrylate, bisphenol F ethylene glycol adduct acrylate, tricyclodecanemethanol diacrylate, trishydroxyethyl isocyanurate diacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, trimethylol propane triacrylate, trimethylolpropane ethylene glycol adduct triacrylate, trimethylolpropane propylene glycol adduct triacrylate , pentaerythritol triacrylate, phosphate Trisacryloyloxyethyl, trishydroxyethyl triacrylate isocyanurate triacrylate modified epsilon-caprolactam, trimethylolpropane ethoxy triacrylate, glycerol propylene glycol adduct triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethylene glycol adduct tetraacrylate, tetraacrylate ditrimethylolpropane, dipentaerythritol hexa (penta) acrylate, pentaacrylate Dipentaerythritolmonohydroxy, acrylic acid , Methacrylic acid, urethane acrylate, epoxy acrylate, polyester acrylate, and / or unsaturated polyester acrylates. Further are Co- and terpolymers of said acrylates with monomers such as styrene, vinyl acetate, ethyl vinyl acetate, itaconic acid and / or vinyl esters of the Kochsäuren suitable.

As starting materials for the sol-gel binder polymers, for example, the following silicon compounds or mixtures thereof can be used, which are selected from the group tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane,

Tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane hydride, triethoxysilane hydride, hydride tripropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , gamma-glycidoxypropyltrimethoxysilane, gamma

Acryloyloxypropyltrimethoxysilane, gamma -Methacryloyloxypropyltri- methoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-diethoxysilane Aminopropylmethyl-, N- (n-butyl) -3- aminopropyltrimethoxysilane, N- (n-butyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-amino- propylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane and / or (3-trimethoxysilylpropyl) -diethylenetriamine. Furthermore, alkylene- or arylene-bridged di-esters are oligosilanes such as 1,2-bis (triethoxysilyl) ethane, l, 2-bis (trimethoxysilyl) ethane, l, 4-phenylenebis (triethoxysilane), l, 4-phenylenebis (trimethoxysilane). In addition, aluminum salts, aluminum alcoholates, zinc salts, zinc alcoholates, zirconium salts, zirconium salts, zirconium alcoholates, titanium salts, titanium alcoholates, iron salts, iron alcoholates, manganese salts or manganese alkoxides can be used as starting materials of the systems.

The binder is preferably prepared in water and / or organic solvents, optionally with the aid of dispersants, in particular in mono-, oligo- or polyfunctional alcohols, particularly preferably in aqueous solutions of the abovementioned alcohols. The crosslinking by hydrolysis of the building blocks and subsequent condensation of the hydrolyzed starting materials is by mineral or organic acids, alkali, organic bases, transition metal catalysts such as titanates and / or zirconates and / or protic solvents, preferably water, because of safety aspects such as flammability and environmental aspects is advantageous, mediated and the binder is obtained as a colloidal solution or dispersion.

Silicone binder polymers usually consist of the repeating unit dimethylsiloxane, which can be supplemented for example by equilibration reactions by other siloxane groups.

The polymer therefore has the structure

R "[- (Y-Si (Me) ₂ ) _n - (Z-Si (RR ') m] -'"

M and n independently assume values between 0 and 100,000. The base unit - (O-Si (Me) ₂ ) - may be partially or completely replaced by units of the type - (O-SiRR ') -, where R and R' may be independently modified and optionally functionalized organic radicals of the alkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl, hydrogen, hydroxyl , May contain amine. The radicals may be attached directly to the central silicon atom or via a heteroatom such as oxygen or nitrogen. The silicon units are connected via a group Y or are directly bonded to each other. Y and Z are independently selected from the aforementioned organic groups or from the group of said heteroatoms. The polymer can carry in end α, ω position end groups R "and / or R '" from the abovementioned groups, which can be chosen independently of one another.

The textile auxiliaries according to the invention can be present as solutions or dispersions in water and / or an organic solvent. Particularly preferred in this invention are aqueous solutions or dispersions of the components, since this is advantageous for process engineering and environmental aspects.

For the preparation of the dispersions or solutions, for example, surface-active substances from the group of anionic, cationic or nonionic surfactants are used. For reasons of compatibility with other textile auxiliaries, the anionic or nonionic, particularly preferably nonionic, surfactants are particularly preferred. To stabilize the preparation further dispersants such as thickeners based on Carboxyalkylpolysaccharide or polyacrylates can be used. The preparation on which the invention is based can be combined with other conventional textile auxiliaries and applied together in standard textile processes. These include, for example, fluorocarbons, plasticizers, high-performance resins, brighteners, dyes, hydrophilizing or hydrophobizing agents, anti-pilling additives, fixers, crosslinkers, surfactants, polymeric binders, adhesives, slip-resistance agents and / or pigments. The textile auxiliaries thus obtained can be used as fleets, foams or pastes for textile finishing. Also, the combination of these additives and the aforementioned components to a preparation according to the invention.

To further improve the washing permanence of the described effect, fixers and / or cross-linkers from the group of blocked and unblocked isocyanates, melamine-formaldehyde resins, urea-formaldehyde resins and / or di-, oligo- or polycarboxylic acids, if appropriate in combination with suitable catalysts, are preferably used in the context of the invention. which increase the reactivity and / or selectivity of the crosslinking used.

In the group of di-, oligo- or polyfunctional carboxylic acids are compounds of the type

W _m (CO ₂ H) _n , where W is an organic radical from the group of optionally functionalized alkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl, m is a number either 0 or 1 and n is a number between 2 and 100000 covers. Alkanedicarboxylic acids are particularly preferred, in particular malonic acid, maleic acid, derivatives succinic and oxalic acid. Particularly suitable oligo- and polycarboxylic acids are alkyloligo-, alkylpoly- or aryloligocarboxylic acids, particular preference is given to butanetetracarboxylic acid, all-cis-1,2,3,4-cyclopentanetetracarboxylic acid, tricarballylic acid, citric acid, 1,2,3-trans-carboxylic acid. Propentricarboxylic acid, succinic acid and derivatives of polyacrylic acid and polymethacrylic acid as homopolymers or copolymers.

Suitable catalysts for the fixers are generally Lewis acids or bases. Magnesium chloride is particularly preferably used alone or in combination with Bronsted acids, preferably orthophosphoric acid, citric acid, sulfuric acid. Alternatively, Brönsted acids, preferably ortho-phosphoric acid, citric acid, sulfuric acid without Lewis acid can be used. Also known is the use of basic catalysts such as amines, hypophosphites, phosphonates, pyro and polyphosphates or alkali.

The textile material according to the invention may be composed of natural fibers such as cotton, bast fibers, hard fibers, wool, silk, mineral fibers and / or synthetic fibers such as cellulose regenerated fibers, polylactic acid, polyester, polyamide, polyimide, polyamideimide, polyphenylene sulfide, aramid, polyvinyl chloride, polyacrylonitrile, Polyvinyl acetal, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, elastane, carbon fibers, silicate fibers, glass fibers, basalt fibers, metal fibers consist, contain these or consist of mixtures of the materials mentioned. Also, laminated fibers or fibers cast in a composite material are according to the invention. The color change of the textile after treatment with the textile auxiliaries according to the invention, measured in the CIE-Lab color space, is very small.

After application of the preparation, the textile according to the invention shows a color change of less than or equal to 10, preferably less than 3, units according to CIE-Lab color space or a maximum degree of whiteness of less than or equal to 6, preferably less than or equal to 3, Berger units.

The textile auxiliaries according to the invention is characterized in particular in that a product refined therewith exhibits a lower remission and / or a higher absorption in the range of the infrared light and / or the solar spectrum or parts thereof.

Furthermore, it is preferably characterized in that it absorbs an increased amount of heat per surface under solar or IR radiation.

The textile according to the invention shows, under irradiation in the measuring apparatus according to FIG. 1, a temperature increase of 5 ° C., preferably of 15 ° C., particularly preferably of 25 ° C., compared to a non-refined reference.

EXEMPLARY EMBODIMENTS:

Carrying out the measurements:

A measuring apparatus consisted of two identical IR lamps with a power of 150 W, a device for clamping the textile samples at a distance of d = 30 cm thereof, the textile samples at an angle of a = 45 ° inclined. The temperature increase of the textiles was measured as a function of the duration of irradiation, whereby a reference sample was always irradiated as a comparison (FIG. 1).

1: Measuring apparatus for determining the temperature increase (side and front view):

In the drawing, two lamps (a), a device for fixing the textile samples (b) at a distance d = 30 cm from the lamps at an angle a = 45 ° are shown.

Fig. 2:

Fig. 2 shows a remission spectrum of an embodiment compared to the reference.

As ΔΤ, the temperature difference after 2 min in the measuring apparatus of Fig. 1 between refined and reference pattern is referred to.

ΔΤ = T (example) - T (reference)

The remission was determined by standard techniques using a Datacolor type instrument, type Microflash 45, preferably at a wavelength of 980 nm. The remission fraction was the quotient of remission of the sample divided by the remission of the reference sample: The optical assessment was carried out in a commercial Abmusterungskabine with different light sources.

Reference Example 1:

White cotton swatches (twill, 205 g / m ² , 20 cm x 30 cm) were set with 250 ml of a fresh finish liquor consisting of 0.45% indium tin oxide added as a 20% pigment dispersion and 5% polyurethane binder polymer in soft water to pH 5.5 with acetic acid, equipped on a laboratory pad. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C. Subsequently, the patterns were measured with a reference pattern in the apparatus shown in Fig. 1, and remission and color numbers were determined.

ΔΤ 15 ° C

Remission share 93%

ΔΕ according to CIE-Lab 11,2

color space

Optical assessment Recognizable

blue shift The sample showed a color change unacceptable to the textile expert. In addition, ITO is not feasible in the required quantities in the textile industry.

Reference Example 2:

White polyamide pattern (screen, 120 g / m ^2, 20 cm x 30 cm) were made with 250 ml of a freshly prepared finishing liquor comprising 1% aluminum zinc oxide (d ₅ o = 50 nm) was added as a 16% dispersion, and 5 % Polyurethane binder polymer in soft water, adjusted to pH 5.5 with acetic acid, equipped on a laboratory pad. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C. Subsequently, the patterns were measured with a reference pattern in the device shown in Figure 1, and remission and color numbers were determined.

The pattern was color acceptable to the textile expert, but the amount of heat absorbed is not sufficient. Embodiment 1:

White PES / lyocell fabrics (210 g / m ² , 20 cm x 30 cm) were coated with 250 ml of a fresh finish liquor consisting of 0.02% conductive organic polymer, 5% polyurethane binder polymer, 1% fixer and 0.5 % Kollasol CDO (surfactant, available from CHT R. Beitlich GmbH), in soft water adjusted to pH 5.5 with acetic acid, on a laboratory pad. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C. Subsequently, the patterns were measured with a reference pattern in the apparatus shown in Fig. 1, and remission and color numbers were determined.

Embodiment 2:

White PES / lyocell fabrics (210 g / m ² , 20 cm x 30 cm) were mixed with 250 ml of a freshly prepared equipment liquor consisting of 0.2% indium tin oxide, 0.02% organically conductive polymers, 5% polyurethane. Binder polymer, 1% fixer, 0.05% Kollasol CDO, adjusted to pH 5.5 in soft water with acetic acid, equipped on a laboratory pad. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C.

Embodiment 3:

Red polyamide samples (twill weave, 120 g / m ² , 20 cm x 30 cm) were mixed with 250 ml of a fresh finish liquor consisting of 0.8% aluminum nitride added as a 20% pigment dispersion containing 0.1% Kollasol CDO Soft water, adjusted to pH 5.5 with acetic acid, equipped on a laboratory pad. In some examples, 0.02% conductive organic polymers were also added. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C. Subsequently, the patterns were with a reference pattern in the apparatus shown in Fig. 1 measured and determined remission and color numbers.

Embodiment 4:

Yellow viscose fabrics (160 g / m ² , 20 cm x 30 cm) were coated with 250 ml of a fresh finish liquor consisting of 0.2% ternary oxide, 0.05% polyaniline, 5% polyurethane binder polymer, 1% fixer, 0.25% Kollasol CDO, adjusted to pH 5.5 in acetic acid with acetic acid, on a laboratory pad. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C.

ITO ATO FTO Without oxide

ΔΤ 19 ° C 15 ° C 6 ° C 5 ° C

Remission share 72% 74% 81% 84%

ΔΕ according to CIE-Lab 4,8 5,0 3,5 3,5 color space Optical unremarkable lighter reddish inconspicuous unremarkable

Assessment of gray tone

Embodiment 5:

Textile samples of various materials (see table below) were each equipped with 250 ml of the liquor mentioned in Example 2 consisting of indium tin oxide and poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate) and Kollasol CDO on a laboratory pad. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C. Subsequently, the samples were measured as unwashed original, after 10 domestic washes (HHW) at 40 ° C with a reference pattern in the device shown in Figure 1 and the remission determined.

Embodiment 6: Yellow polyester-elastane textile samples were each equipped with 250 ml of the below-mentioned liquors on a laboratory pad. The contact pressure of the rolls was set to 3 bar. After finishing, the fabric was dried on a laboratory fixture frame for 2 minutes at 120 ° C and then condensed for 1 minute at 150 ° C. Subsequently, the patterns were measured with a reference pattern in the device shown in Figure 1 and the remission determined.

# Fleet composition ΔΤ Remissions Optical

share assessment

1 5% polyurethane binder103% unobtrusive

polymer I, 0.1% Kollasol CDO

2 5% polyurethane binder23 ° C 78% light gray polymer I, shift

0.4% antimony tin oxide, 0.1%

Polyaniline, 0.1% Kollasol CDO

3 5% polyurethane binder28 ° C 72% low

polymer I, gray-blue

0.4% indium tin oxide, 0.1% color polyaniline, 0.1% Kollasol CDO shift

4 5% polyurethane binder2 ° C 102% unobtrusive

Polymer II, 0.1% Kollasol

CDO

5 5% polyurethane binder16 ° C 88% light gray polymer II, shift

0.4% antimony tin oxide, 0.1%

Polyaniline, 0.1% Kollasol CDO

6 5% polyurethane binder18 ° C 84% low

polymer II, gray-blue

0.4% indium tin oxide, 0.1% color polyaniline, 0.1% Kollasol CDO shift

7 2% sol-gel binder (iSys MTX) 0 ° C 101% unremarkable 2% sol-gel binder (iSys 22 ° C 81% marginal MTX), gray

0.4% antimony tin oxide, 0.1% polyaniline, 0.1% Kollasol CDO

2% sol-gel binder (iSys 26 ° C 78% marginal MTX), gray-blue

0.4% indium tin oxide, 0.1% color polyaniline, 0.1% Kollasol CDO shift

Claims

claims:

1. Textile auxiliaries for IR absorption and / or reflection of textiles, containing

(a) at least one semiconductor,

(d) solvent and / or further dispersing aids.

2. Textile auxiliaries according to claim 1 comprising at least one semiconductor selected from one of the following groups, comprising the following compounds a) - A ^m B ^v semiconductor comprising compounds of the binary type, wherein A is gallium, indium, thallium, germanium, tin , Lead and B are nitrogen, phosphorus, arsenic, antimony and bismuth in any desired stoichiometric ratios, b) elemental semiconductors, in particular modifications of tin, indium, carbon, silicon and germanium c) conductive organic polymers, in particular polypyrrole, polyaniline, Polyparaphenylene, polythiophene, poly (4,4-dioctylcyclopentadithiophene), poly (3,4-ethylenedioxythiophene) or poly (3,4-ethylene dioxythiophene) / poly (styrenesulfonate) and

d) - a semiconductor from the group of transparent conductive oxides of the type A _n D _m O _x , where A can be fluorine, indium, magnesium, aluminum, chromium, zinc or antimony and D-zinc, titanium or tin, and n a Number between 0 and 1 and m = ln, where x is the In particular, it comprises the compounds indium tin oxide, antimony tin oxide, aluminum zinc oxide, magnesium zinc oxide, fluorine-doped tin oxide or mixtures of the binary oxides of these metals.

3. Textile auxiliaries according to claim 2, characterized in that the semiconductors are selected from at least one of the semiconductors of groups a), b) and c) and furthermore at least one semiconductor from group d), or mixtures of at least two semiconductors selected from the Groups a), b) and c), in particular at least one from group a) and at least one from group c).

4. Textile auxiliaries according to one of claims 1 to 3, characterized in that the said components dissolved in organic solvents, water or a mixture of the aforementioned solvents, dispersed, colloidally or finely dispersed.

5. Textile auxiliaries according to one of claims 1 to 4, characterized in that it further comprises fixers and / or crosslinking agents, in particular di-, oligo- or polycarboxylic acids, melamine-formaldehyde resins, urea-formaldehyde resins, blocked and / or unblocked isocyanates.

6. Textile auxiliaries according to one of claims 1 to 5, characterized in that it further fluorocarbons, plasticizers, high-performance resins, brighteners, dyes, hydrophilizing or hydrophobing agents, anti-pilling additives, adhesives, anti-slip agents, biocides, thickeners, crosslinkers, fixers, Fungicides and / or pigments may have.

7. Use of a textile auxiliaries according to one of claims 1 to 6, in the exhaust or by forced application such as coating, equipment by padding, printing, spray process, monofilament application and / or dyeing, generally for finishing textiles, textile fabrics, nonwovens, fibers, threads or composites of one or more such precursors containing natural and / or synthetic fibers.

8. Natural fibers, including textiles made thereof, coated with a textile auxiliary according to one of claims 1 to 7, containing cotton, bast fibers, hard fibers, wool, silk and / or mineral fibers and mixtures thereof.

9. Synthetic fibers including textiles made therefrom coated with a textile auxiliary according to any one of claims 1 to 6 comprising fibers selected from regenerated cellulose fibers, polylactic acid, polyester, polyamide, polyimide, polyamideimide, polyphenylene sulfide, aramid, polyvinyl chloride, polyacrylonitrile, polyvinyl acetal, polytetrafluoroethylene, polyethylene , Polypropylene, polyurethane, elastane, carbon fibers, silicate fibers, glass fibers, basalt fibers and / or metal fibers and mixtures thereof.

10. Fibers including the textiles made therefrom according to claim 8 and / or 9 comprising natural fibers and synthetic fibers.