EP2859145B1 - Textile auxiliary agent and textile product finished therewith - Google Patents

Description

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.

The use of IR absorbing and / or reflecting layers of different materials such as aluminum or carbon has been used in JP 2005212471 tried to solve the problem.

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 are described in the patent application JP 2005290585 radiation-absorbing layers applied to textiles. This problem solution is very costly and technically complex.

In EP 1 792 724 A2 The two-sided coating is described with a tourmaline tape to reduce the emission of 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.

Recording thermal radiation by using dark dyes describes the patent application JP 2009062652 , In EP 1 847 635 A1 describes the use of IR-reflecting pigments based on activated tungsten oxides. Organic bisiminium compounds are disclosed in Japanese Patent Application JP 2009203596 used to produce IR-absorbent 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. As a result, the authors achieve an improvement in the Thermal insulation. The Japanese patent JP 2004149931 describes the use of zirconium carbide, titanium oxide or specific 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. So describes WO 01/25367 A1 hydrothermal production of such oxides and the use thereof to produce textiles with sensor properties or antistatic effects. Already in EP 0 341 554 A1 For example, large quantities of such oxides are added to synthetic fibers in a masterbatch application to produce conductive textiles. In order to achieve angle - dependent color effects of textiles, TW 201113410 Indium tin oxide used 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. So for example describes DE 10 258 014 A1 a method for the introduction of glass fibers unilaterally coated with aluminum powder in heat-curing blankets, in order to enable visual-optical camouflage by reducing the emitted heat 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 in WO 2004/020931 A1 shown. 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 disclosed in US Pat WO 2010/120531 A1 described.

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

The influence especially black textiles is in WO 2009/118419 A1 described. 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 aids for IR absorption and / or reflection and the use of semiconductors indium tin oxide and antimony tin oxide.

DE 39 21 249 A1 describes IR-absorbent textiles that are resistant to detection by indulgence devices with IR-absorbing compounds that are conjugated organic polymers.

WO 2008/004993 A2 describes layers with near infrared absorptions 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.

• (α) Halbleiter, die ausgewählt sind aus wenigstens einem der Halbleiter der Gruppen a), b) und c) sowie weiterhin wenigstens einem Halbleiter aus der Gruppe d) oder Mischungen von wenigstens zwei Halbleitern ausgewählt aus den Gruppen a), b) und c), insbesondere wenigstens einen aus der Gruppe a) sowie wenigstens einen aus der Gruppe, c) wobei
  1. a) A^IIIB^V-Halbleiter Verbindungen des binären Typs umfasst, wobei A für Gallium, Indium, Thallium, Germanium, Zinn, Blei und B für Stickstoff, Phosphor, Arsen, Antimon und Bismut in beliebigen stöchiometrischen Verhältnissen steht,
  2. b) elementare Halbleiter ausgewählt aus Modifikationen des Zinns, Indiums, Kohlenstoffs, Siliziums und Germaniums umfasst,
  3. c) Polypyrrol, Polyanilin, Polyparaphenylen, Polythiophen, Poly(4,4-dioctyl-cyclopenta-dithiophene), Poly(3,4-ethylen-dioxythiophen) oder Poly(3,4-ethylen-dioxythiophen) / Poly(styrolsulfonat) umfasst,
  4. d) einen Halbleiter aus der Gruppe, Indiumzinnoxid, Antimonzinnoxid, Aluminiumzinkoxid, Magnesiumzinkoxid, fluordotiertes Zinnoxid oder Mischungen der binären Oxide dieser genannten Metalle umfasst,
• (β) einen oder mehrere Binderpolymere aus der Gruppe der Polyurethane, Polyacrylate, Styrol-Butadiene, Silikone, Siloxane, Sol-Gele, Polyvinylchlorid, Ethylvinylacetat, Epoxy- oder Polyesterharze,
• (γ) oberflächenaktive Substanzen ausgewählt aus der Gruppe der anionaktiven, kationaktiven oder nicht-ionischen Tenside sowie
• (δ) Lösungsmittel und/oder weitere Dispergierhilfsmittel.

The invention in a first embodiment, a textile auxiliary for IR absorption and / or reflection of textiles, containing

• (α) semiconductors which 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 the group, c) where
  1. a) A ^III B ^V semiconductor comprises compounds of the binary type, wherein A stands for gallium, indium, thallium, germanium, tin, lead and B for nitrogen, phosphorus, arsenic, antimony and bismuth in any desired stoichiometric ratios,
  2. b) elemental semiconductors selected from modifications of tin, indium, carbon, silicon and germanium,
  3. c) polypyrrole, polyaniline, polyparaphenylene, polythiophene, poly (4,4-dioctyl-cyclopenta-dithiophene), poly (3,4-ethylene-dioxythiophene) or poly (3,4-ethylene-dioxythiophene) / poly (styrenesulfonate) .
  4. d) a semiconductor from the group, indium-tin oxide, antimony-tin oxide, aluminum-zinc oxide, magnesium-zinc oxide, fluorine-doped tin oxide or mixtures of the binary oxides of said metals,
• (β) 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,
• (γ) surfactants selected from the group of anionic, cationic or nonionic surfactants and
• (δ) solvent and / or other dispersing aids.

The present invention combines the simplicity of already existing textile-technological processes such as equipment by means of pad-forced application, coating by means of pastes or foams, spray application, printing, dipping and exhausting processes and single filament application on Galette or in the dipping bath with an effect of increased heat energy absorption or reduced heat emission (Fig. loss) of such refined textiles by selection 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 the application of the invention, such a finished textile under the influence of electromagnetic radiation heats significantly more than a corresponding comparative sample of the same parameters (e.g., material composition, color, fabric weight, thickness, texture and weave). At the same time, this can be used to detect a reduction in the remission of electromagnetic radiation and / or an increase in 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. In the former group a) fall the compounds of the A ^III 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.

For the purposes of this invention, the group A ^III B ^V- semiconductor group comprises the compounds AB of elements A, where A is gallium, indium, thallium, germanium, tin, lead and B is nitrogen, phosphorus, arsenic, antimony and bismuth in stand 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, namely polypyrrole, polyaniline, polyparaphenylene, polythiophene, poly (4,4-dioctylcyclopentadithiophene), poly (3,4-ethylenedioxythiophene) or poly (3,4-ethylenedioxythiophene) / poly ( styrenesulfonate), as semiconductors solve the technical problem.

Suitable oxides from group d) are fluorine-doped tin oxide, indium tin oxide, antimony tin oxide, aluminum zinc oxide, magnesium zinc oxide or mixtures of the binary oxides of these metals. 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. 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).

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 in 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 ^-1 · Cm ^-1 . Particularly preferably, the infrared-absorbing material has an absorption maximum in a range of 900 to 1000 nm. In particular, a material selected from phthalocyanines, naphthalocyanines, anthraquinones, cyanine compounds, squalylium compounds, thiolnickel complex compounds, triallylmethanes, naphthoquinones, anthraquinones and amine compounds such as N, N, N ', N'-tetrakis is used as the organic infrared ray absorbing material (p-di-n-butylaminophenyl) -p-phenylenediaminium perchlorate, phenylenediaminium chlorate, phenylenediaminium hexafluoroantimonate, phenylenediaminium fluoroborate, phenylenediaminium fluorate and phenylenediaminium perchlorate.

The particulate semiconductors used in this invention have a particle size (number average, d ₅₀ , laser diffraction) of 1 nm to 10 .mu.m, preferably less than 2 microns, 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, for example by W. Siefken in Justus Liebig's 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 having 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 also 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-durene diisocyanate (DDI), 4,4'-stilbenediisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI) 2,4- and 2,6-tolylene diisocyanate (TDI) and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate (MDI), and / or naphthylene-1, 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 are described, m- and p-Isocyanatophenylsulfonylisocyanate according to U.S. Patent 3,454,606 perchlorinated aryl polyisocyanates, as in U.S. Patent 3,277,138 Carbodiimidgruppen containing polyisocyanates, as described in U.S. Patent 3,152,162 as in DE-OS 25 04 400 . 25 37 685 and 25 52,350 Norbornane diisocyanates according to U.S. Patent 3,492,301 , Allophanatgruppen containing polyisocyanates, as described in GB-PS 994 890 , of the BE-PS 761 626 and NL-A 7 102 524 be described, having isocyanurate polyisocyanates, as described in U.S. Patent No. 3,001,971 , in DE-PS 10 22 789 . 12 22 067 and 10 27 394 as in DE-OS 19 29 034 and 20 04 048 urethane-containing polyisocyanates, as described for example in the BE-PS 752 261 or in U.S. Patent 3,394,164 and 3 644 457 be described, acylated urea groups having polyisocyanates according to DE-PS 12 30 778 Biuret group-containing polyisocyanates as described in U.S. Patent 3,124,605 . 3,201,372 and 3 124 605 as in British Patent 889,050 are described by telomerization reactions prepared polyisocyanates, as described in U.S. Patent 3,654,106 are described, polyisocyanates containing ester groups, as in GB-PS 965 474 and 1 072 956 , in U.S. Patent 3,567,763 and in DE-PS 12 31 688 be mentioned, reaction products of the above isocyanates with acetals according to DE-PS 10 72 385 and polymeric fatty acid ester-containing polyisocyanates according to U.S. 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 group-containing polyisocyanates ("modified polyisocyanates"), in particular those modified polyisocyanates 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 ally 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 (meth) 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 l (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, tetrahydrofurfuryl (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, acryloyloxyethyl phthalic acid, tribromoph enyl acrylate, tribromophenol ethoxylated (meth) acrylate, methyl methacrylate, tribromophenyl methacrylate, methacryloxyethyl acid, methacryloyloxyethylmaleic acid, methacryloyloxyethylhexahydrophthalic acid, methacryloyloxyethylphthalic acid, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, beta-carboxyethyl acrylate, N-methylol acrylamides, N- methoxymethyl acrylamide, 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 phosphate, Bisphenol ethylene glycol adduct acrylate, Bisphenol ethylene glycol adduct acrylate, Tricyclodecanemethanol diacrylate, Trishydroxyethyl isocyanurate diacrylate, 2-Hydroxy-1-acryloxy-3 -methacryloxypropan, trimethylolpropane triacrylate, trimethylol propane ethylene glycol adduct triacrylate, trimethylol propane propylene glycol adduct triacrylate, pentaerythritol triacrylate, Trisacryloyloxyethyl phosphate, trishydroxyethyl isocyanurate triacrylate, triacrylate modified epsilon-caprolactam, trimethylolpropane ethoxy triacrylate, glycerol propylene glycol adduct triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethylene glycol adduct tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxy pentaacrylate, acrylic acid, methacrylic acid, urethane acrylate, epoxyacrylate, polyester acrylate, and / or unsaturated polyester acrylates. Further, copolymers and terpolymers of said acrylates with monomers such as styrene, vinyl acetate, ethyl vinyl acetate, itaconic acid and / or vinyl esters of the cooking acids are suitable.

Examples of suitable starting materials for the sol-gel binder polymers are the following silicon compounds or mixtures thereof selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane , Tetra-tert-butoxysilane, trimethoxysilane hydride, triethoxysilane hydride, tripropoxysilane hydride, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, Butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-acryloyloxypropyl trimethoxysilane, gamma -methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (n-butyl) -3-aminopropyltrimethoxysilane, N- (n-butyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl-methyldiethoxysilane and / or (3-trimethoxysilylpropyl) -diethylenetriamine. Also suitable are alkylene- or arylene-bridged di- or oligosilanes, such as 1,2-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) ethane, 1,4-phenylenebis (triethoxysilane), 1,4-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 by mineral or organic acids, alkali, organic bases, transition metal catalysts, such as titanates and / or zirconates and / or protic solvents, preferably water, since this is advantageous for safety aspects such as flammability and environmental aspects, and gives the binder 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 ] -R"'

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 type , Aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl, hydrogen, hydroxyl, 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 hydrophobing agents, anti-pilling additives, fixers, crosslinkers, surfactants, polymeric binders, adhesives, anti-slip 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 effect described, fixers and / or cross-linking agents from the group of blocked and unblocked are preferably used in the context of the invention Isocyanates, melamine-formaldehyde resins, urea-formaldehyde resins and / or di-, oligo- or polycarboxylic acids, if appropriate in combination with suitable catalysts which increase the reactivity and / or selectivity of the crosslinking.

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

W _m (CO ₂ H) _n

wherein W is an organic radical selected from the group of optionally functionalized alkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl, m as a number is either 0 or 1 and n is a number between 2 and 100,000. Alkanedicarboxylic acids are particularly preferred, in particular malonic acid, maleic acid, derivatives of succinic acid 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-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 ortho-phosphoric 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 Fig. 1 a temperature increase of 5 ° C, preferably 15 ° C, particularly preferably 25 ° C, compared to a non-refined reference.

Exemplary embodiments: Carrying out the measurements:

• Fig. 1: Messapparatur zur Bestimmung der Temperaturerhöhung (Seit-und Frontalansicht):
  • In der Zeichnung sind zwei Lampen (a), eine Vorrichtung zur Fixierung der textilen Proben (b) in einem Abstand d = 30 cm von den Lampen in einem Winkel α=45° gezeigt.
• Fig. 2:
  Fig. 2 zeigt ein Remissionspektrum eines Ausführungsbeispiels im Vergleich zur Referenz.

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 being inclined at an angle of α = 45 °. 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 ).

• Fig. 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 α = 45 ° are shown.
• Fig. 2 :
  Fig. 2 shows a remission spectrum of an embodiment compared to the reference.

As ΔT, the temperature difference after 2 min in the measuring apparatus after Fig. 1 between refined and reference pattern. $$\mathrm{.DELTA.T}=\mathrm{T}\left(\mathrm{example}\right)-\mathrm{T}\left(\mathrm{reference}\right)$$

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: $$\mathrm{Remission\; share}\left[\%\right]=\frac{\mathrm{Remission\; at}980\mathrm{nm\; of\; the\; pattern}}{\mathrm{Remission\; at}980\mathrm{nm\; of\; the\; reference}}$$

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 Rolling was set at 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 with a reference pattern in the in Fig. 1 measured device as well as remission and color numbers determined. .DELTA.T 15 ° C Remission share 93% ΔE according to CIE-Lab color space 11.2 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 samples (canvas, 120 g / m ² , 20 cm x 30 cm) were coated with 250 ml of a freshly prepared equipment liquor consisting of 1% aluminum zinc oxide (d ₅₀ = 50 nm) 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 with a reference pattern in the in illustration 1 measured device as well as remission and color numbers determined. .DELTA.T 2 ° C Remission share 96% ΔE according to CIE-Lab color space 2 Optical assessment inconspicuous

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, 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 with a reference pattern in the in. Fig. 1 measured device as well as remission and color numbers determined. Poly (3,4-ethylene dioxythiophene) / poly (styrenesulfonate) polyaniline polypyrrole .DELTA.T 5 ° C 5 ° C 3 ° C Remission share 86% 88% 96% ΔE according to CIE-Lab color space 4.1 5.0 5.3 Optical assessment inconspicuous inconspicuous slight gray shift

Embodiment 2:

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 0.2% indium tin oxide, 0.02% organic conductive polymers, 5% polyurethane binder polymer, 1 % Fixer, 0.05% Kollasol CDO, adjusted to pH 5.5 in soft water 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. Poly (3,4-ethylene dioxythiophene) / poly (styrenesulfonate) polyaniline polypyrrole .DELTA.T 19 ° C 11 ° C 12 ° C Remission share 75% 82% 81% ΔE according to CIE-Lab color space 7.7 8.5 10.0 Optical assessment inconspicuous inconspicuous slight gray shift

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 with a reference pattern in the in Fig. 1 measured device as well as remission and color numbers determined. Without conductive organic polymer Poly (3,4-ethylene dioxythiophene) / poly (styrenesulfonate) polyaniline polypyrrole .DELTA.T 8 ° C 15 ° C 10 ° C 9 ° C Remission share at λ = 980 nm 77% 62% 75% 75% ΔE according to CIE-Lab color space 3.8 4.1 4.2 8.0 Optical assessment inconspicuous inconspicuous inconspicuous slight gray shift

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 .DELTA.T 19 ° C 15 ° C 6 ° C 5 ° C Remission share 72% 74% 81% 84% ΔE according to CIE-Lab color space 4.8 5.0 3.5 3.5 Optical assessment inconspicuous slight reddish gray tone inconspicuous inconspicuous

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 taken as unwashed original, after 10 household washes (HHW) at 40 ° C with a reference pattern in the illustration 1 Measured device measured and determines the remission. Material before washes Material after 10 HHW polyester / Spandex Polyamide polyester / Spandex Polyamide primary color White White White White goods weight 130 g / m ² 230 g / m ² 130 g / m ² 230 g / m ² .DELTA.T 24 ° C 32 ° C 22 ° C 30 ° C Remission share 82% 74% 83% 77% ΔE according to CIE-Lab color space 4.5 7.5 3.6 6.6

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 with a reference pattern in the in illustration 1 Measured device measured and determines the remission. # fleet composition .DELTA.T Remission share Optical assessment 1 5% polyurethane binder polymer I, 0.1% Kollasol CDO 103% inconspicuous 2 5% polyurethane binder polymer I, 0.4% antimony tin oxide, 0.1% polyaniline, 0.1% Kollasol CDO 23 ° C 78% slight gray shift 3 5% polyurethane binder polymer I, 0.4% indium tin oxide, 0.1% polyaniline, 0.1% Kollasol CDO 28 ° C 72% slight gray-blue color shift 4 5% Polyurethane Binder Polymer II, 0.1% Kollasol CDO 2 ° C 102% inconspicuous 5 5% Polyurethane Binder Polymer II, 0.4% antimony tin oxide, 0.1% polyaniline, 0.1% Kollasol CDO 16 ° C 88% slight gray shift 6 5% polyurethane binder polymer II, 0.4% indium tin oxide, 0.1% polyaniline, 0.1% Kollasol CDO 18 ° C 84% slight gray-blue color shift 7 2% sol-gel binder (iSys MTX) 0 ° C 101% inconspicuous 8th 2% sol-gel binder (iSys MTX), 0.4% antimony tin oxide, 0.1% polyaniline, 0.1% Kollasol CDO 22 ° C 81% marginal gray shift 9 2% sol-gel binder (iSys MTX), 0.4% indium tin oxide, 0.1% polyaniline, 0.1% Kollasol CDO 26 ° C 78% marginal gray-blue color shift

Claims (9)

1. A textile auxiliary agent for IR absorption and/or reflection in textiles, containing

   (α) semiconductors selected from at least one of the semiconductors of groups a), b) and c), and further at least one semiconductor from group d), or mixtures of at least two semiconductors selected from groups a), b) and c), especially at least one from group a) and at least one of group c), wherein

   a) includes A^IIIB^V semiconductor compounds of the binary type, wherein A represents gallium, indium, thallium, germanium, tin, lead, and B represents nitrogen, phosphorus, arsenic, antimony and bismuth in any stoichiometric ratios,

   b) includes elemental semiconductors selected from allotropes of tin, indium, carbon, silicon and germanium,

   c) includes polypyrrole, polyaniline, polyparaphenylene, polythiophene, poly(4,4-dioctylcyclopentadithiophene), poly(3,4-ethylenedioxythiophene) or poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate),

   d) includes a semiconductor from the group of indium tin oxide, antimony tin oxide, aluminum zinc oxide, magnesium zinc oxide, fluorine-doped tin oxide or mixtures of the binary oxides of these mentioned metals,

   (β) 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,

   (γ) surface-active substances selected from the group of anion-active, cation-active or non-ionic surfactants, and

   (δ) solvents and/or other dispersing aids.
2. The textile auxiliary agent according to claim 1, characterized in that said semiconductors are selected from at least one from group a) and at least one from group c).
3. The textile auxiliary agent according to claim 1 or 2, characterized in that the components mentioned are in a form dissolved, dispersed, colloidal or finely dispersed in organic solvents, water or a mixture of the above mentioned solvents.
4. The textile auxiliary agent according to any of claims 1 to 3, characterized by further comprising fixatives and/or cross-linking agents, especially di-, oligo- or polycarboxylic acids, melamine formaldehyde resins, urea formaldehyde resins, blocked and/or unblocked isocyanates.
5. The textile auxiliary agent according to any of claims 1 to 4, characterized in that it may further comprise fluorocarbons, softeners, brighteners, colorants, hydrophilizing or hydrophobizing agents, anti-pilling additives, adhesives, antislip agents, biocides, thickeners, cross-linking agents, fixatives, fungicides and/or pigments.
6. Use of a textile auxiliary agent according to any of claims 1 to 5 in an exhaust process by forced application, such as coating, finishing by padding, pressure, spray methods, single thread application and/or dyeing, generally for the finishing of textiles, textile scrims, non-wovens, fibers, threads or composites, one or more of such precursor products containing natural and/or synthetic fibers.
7. Natural fibers including the textiles made therefrom, coated with a textile auxiliary agent according to any of claims 1 to 6, containing cotton, bast fibers, hard fibers, wool, silk, and/or mineral fibers, and mixtures thereof.
8. Synthetic fibers including the textiles made therefrom, coated with a textile auxiliary agent according to any of claims 1 to 7, containing fibers selected from cellulose regenerate fibers, polylactic acid, polyester, polyamide, polyimide, polyamideimide, polyphenylene sulfide, aramid, polyvinyl chloride, polyacrylonitrile, polyvinyl acetal, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, elasthane, carbon fibers, silicate fibers, glass fibers, basalt fibers, and/or metal fibers, and mixtures thereof.
9. Fibers including the textiles made therefrom according to claim 7 and/or 8, comprising natural fibers and synthetic fibers.

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