DE102010002232A1 - Benzophenone-containing dispersions for textile applications - Google Patents

Abstract

The present invention describes a composition as an aqueous dispersion of benzophenone-containing (meth) acrylate polymers. The invention relates to the use of the aqueous dispersions described for textile applications, in particular for nonwoven bonding.

Description

Field of the invention

The present invention describes a composition herein as an aqueous dispersion of benzophenone-containing (meth) acrylate polymers. The invention relates to the use of the described aqueous dispersions for textile applications, in particular for nonwoven bonding.

State of the art

For textile applications, in particular for nonwoven bonding, thermosetting dispersions are frequently used. A chemical basis is the combination of methacrylamide, methacrylic acid and N-methylolmethacrylamide as a crosslinking system. There are also the corresponding systems based on acrylate. The nonwoven fabric impregnated with such a dispersion is thermally treated (140 ° C.). In this case, a covalent crosslinking occurs. A disadvantage of this crosslinking system is the release of formaldehyde during crosslinking. In addition, according to experience, these dispersions are not very shear-stable, which can lead to problems with the application to the textiles.

Polyacrylate dispersions are known in principle. For quite some time, such dispersions have been used to coat various substrates to seal and protect them. One exemplary application relates to the sealing of mineral substrates such as stones, concretes, concrete roof tiles, conventional bricks and the like (cf. U.S. Patent 4,511,699 as well as the British Patent 1,411,268 ).

From the EP 0 355 028 A1 For example, a process is known in which substrates are coated on their surfaces with aqueous polyacrylate dispersions and the coatings are then dried at elevated temperature. Here, a mixture is used for the coating of A) a 20 to 65 wt .-%, a minimum film-forming temperature of -30 to + 30 ° C having aqueous dispersion of a copolymer of a) 20 to 70% of its weight of (meth) acrylic esters b) from 30 to 60% of its weight of styrene, alpha-methylstyrene, methyl methacrylate, tert-butyl (meth) acrylate and / or (meth) acrylonitrile and c) from 0.2 to 7% of its weight of 3 to 5 C atoms unsjsenden mono- and / or dicarboxylic acids and / or their optionally substituted on the N-atom by an alkyl group containing 1 to 4 carbon atoms substituted amides and B) 0 , 1 to 5 wt .-%, based on the amount of the copolymer contained in the component (A), of an aromatic ketone. The mixture is then exposed to ultraviolet light for curing before or after drying.

Come as aromatic ketone according to the EP 0 355 028 A1 for example, benzophenone and benzophenone derivatives such as 3,3'-dimethyl-4-methoxybenzophenone, 3, - and 4-hydroxybenzophenone, benzophenone-2-carboxylic acid, benzophenone-3-carboxylic acid, benzophenone-4-carboxylic acid and the like, and 2-, 3 and 4-phenylbenzophenone, 2-, 3- and 4-alkylbenzophenones having 1 to 10 C atoms in the alkyl radicals, such as 2-, 3- and 4-methylbenzophenone, 2-, 3-, 4-nonylbenzophenone, dialkylbenzophenones and also olefinically unsaturated and water-soluble benzophenone derivatives in question.

Although the coatings of the EP 0 355 028 A1 Nevertheless, the coatings are still in need of improvement, in particular with regard to properties such as resistance to, inter alia, weathering, to solvents, to organic and inorganic chemicals, and to properties such as hardness of the coating, drying rate of the coating and more. Because of these properties, the dispersions described are unsuitable for solidifying textiles, in particular nonwovens.

Benzophenone and low molecular weight benzophenone derivatives are common photoinitiators. Upon irradiation, radicals form, which can cause the polymerization or crosslinking of ethylenically unsaturated monomers.

Carlini et al. Report in Polymer, 1983, Vol. 24, May, page 599 ff. of polymers containing benzophenone chromophores in the side chain and their use as highly effective photoinitiators. Copolymers of acryloxybenzophenone with menthyl acrylate, methyl acrylate or 1-acryloxy-2-ethoxyethane are disclosed. The copolymers described have about 10 to 90 mol% of acryloxybenzophenone units and are suitable for the photoinitiation of the polymerization. An exact specification of the molecular weight of the presented photoinitiators does not take place in the cited publication.

The US 5,900,472 A describes copolymerizable benzophenone photoinitiators. Benzophenone derivatives having two to four (meth) acrylate groups are shown as well as UV-curable coatings which are obtainable by reaction of the polyvalent benzophenone derivatives with (meth) acrylate under the action of radiation. Of the US 5,900,472 A Accordingly, the coatings obtainable using the polyhydric benzophenones are superior to the heretofore known coatings with known photoinitiators in that they show a reduced tendency to "bleed" (migration). To date, unexploited photoinitiator has tended to suffer from this phenomenon, limiting its use to a few possibilities, including the use of coating or impregnating textiles.

In WO 2002100912 UV-curable aqueous dispersions for coating cellulose, in particular for hygiene articles, are described. The goal here is to improve the resistance to water. On the coating or impregnation of textiles, this system is not transferable due to completely different material requirements and a completely different purpose of the coating.

In DE 1 720 603 and in DE 1 720 605 Polyvinyl acetates with copolymerized benzophen-funtkionellen acrylates for use as a textile impregnating agent described. Disadvantage of polyvinyl acetates, however, is the saponification tendency in the alkaline. Also of disadvantage are the partially crystalline character and the high glass transition temperature, which can lead to an unwanted stiffening of the fibers. In DE 1 720 605 In addition, a dispersion with 54 wt .-% butyl acrylate, 41 wt .-% methyl methacrylate and 4.5 wt .-% of a benzophenone acrylamide disclosed. The high MMA content and the hardness of acrylamides also lead to particularly stiff chains.

task

In view of the prior art mentioned and discussed above, it was an object of the invention to provide novel compositions for the coating of textiles, in particular for use as a consolidator for nonwovens.

The composition itself should be as simple and as versatile as possible or applicable. The composition should comply with all labor regulations and, above all, be as safe as possible in terms of health. In this context, attention should also be paid to the VOC-freedom (no volatile organic compounds) of the composition.

In addition, the coatings should harden and / or dry as quickly as possible and as completely as possible, and the processed textiles or nonwovens should have a longer useful life. For this purpose, the best possible, that is complete and intensive crosslinking of the coating during curing should be achieved.

Other tasks not explicitly mentioned emerge from the overall context of the following description, claims and examples.

solution

The invention relates to the use of benzophenone methacrylate instead of the above-described crosslinking system based on the combination of methacrylamide, methacrylic acid and N-methylolmethacrylamide for coating or impregnating nonwovens and / or textiles. Such systems are not thermally crosslinked by means of UV light. The user is thus able to perform a formaldehyde-free crosslinking after the coating or impregnation of a textile surface fabric, in particular a textile or a nonwoven fabric. It can crosslink relatively quickly by means of UV after predrying of the dispersion on the nonwoven fabric, which additionally leads to a time saving compared to thermally curing systems.

Furthermore, the benzophenone-containing polymethacrylate dispersions according to the invention are significantly more shear-stable than the N-methylolmethacrylamide-containing systems. The results also show a good resistance to cooking and Triwäsche, without any undesirable side reactions, such as a further, subsequent curing, the z. B. observed in the study of the N-methylol-containing reference, occur. Under Triwäsche is understood in the context of this patent, the chemical cleaning with trichlorethylene. These results are based on other chemical cleaning methods or dry cleaning methods, eg. B. with perchlorethylene transferable.

In particular, the objects are achieved by using an aqueous dispersion described below, containing particularly soft, benzophenone-functional poly (meth) acrylates, for coating and / or impregnating textiles or nonwovens:
Textiles are generally understood to mean flexible materials which are composed of a fiber composite. These may be composed of fibers or yarns and z. B. as a woven, knitted or knitted fabric. Synonymous terms for textiles in the clothing industry are fabric or cloth. As a rule, textiles consist of animal fibers such as silk, wool or horsehair; from vegetable fibers such as cotton, bast, hemp, flax, linen fibers, jute, nettle, sisal or coconut fibers; of synthetic polymers such as polyamides, polyesters, polyimides, polypropylene, or polyethylene; from mineral fibers such as asbestos, mineral wool or basalt; or mixtures of different fibers. The preparation can be done for example by means of weaving or knitting. In addition to the clothing industry, textiles can also be used, for example, in the home, furniture, construction, automotive, fire protection or technical textile industries in various other industrial sectors.

Nonwovens are textile fabrics made of individual fibers. The term nonwoven in this text implies simultaneously nonwovens, which are usually unconsolidated nonwovens. Also included is the widely used term nonwovens for nonwovens. The nonwovens may be both tangled and fiber oriented nonwovens. Nonwovens may be formed from mineral fibers such as glass, asbestos, mineral wool or basalt; made from animal fibers such as silk or wool; from vegetable fibers such as cotton; from modified vegetable fibers such as cellulose; of synthetic polymers such as polyamides, polyesters, PVC, polypropylene, polyethylene, polyphenylene sulfide, polyacrylonitrile, polyimide, polytetrafluoroethylene, Nomex, Kevlar or polyamideimide; or mixtures of different fibers. The production can be carried out by means of spinning processes, in particular dry, wet, melt or matrix spinning, or by solidification processes, in particular mechanical, chemical or thermal solidification processes.

In addition to nonwovens or nonwovens, the inventive method can also be applied to felts and / or wadding.

• a) 0,5 bis 25,0 Gewichtsprozent wenigstens einer Verbindung der allgemeinen Formel (I), vorzugsweise eines Benzophenon(meth)acrylats,
  
  worin R¹ Wasserstoff oder Methyl, bevorzugt Methyl bedeutet; R² für Sauerstoff steht; R³ für einen Rest der allgemeinen Formel II steht
  
  worin R⁷, R⁸, R⁹ unabhängig voneinander Wasserstoff oder Methyl sind, n eine ganze Zahl von Null bis zweihundert ist, o und p unabhängig voneinander eine ganze Zahl von Null bis zwei sind, wobei für den Fall, dass die Summe von n und o und p Null ist, R³ eine Bindung ist; R⁴ eine Bindung, Sauerstoff oder O-CO-C, bevorzugt eine Bindung ist; R⁵ für Wasserstoff, Halogen oder einen eins bis zwanzig Kohlenstoffatome aufweisenden Rest steht, der gegebenenfalls mit Sauerstoff, Stickstoff und/oder Schwefel substituiert ist, wobei m für eine ganze Zahl von eins bis vier steht; und R⁶ für einen Aryl- oder Heterocyclylrest, bevorzugt für einen Phenylrest steht; und
• b) eine Mischung weiterer Verbindungen darstellt, bestehend aus 40,0 bis 99,5 Gew.-% unfunktioneller Acrylaten, die von a) verschieden sind, 0 bis 59,5 Gew.-% unfunktioneller Methacrylate, die von a) verschieden sind, und/oder Styrol, 0 bis 5,0 Gew.-% Acrylsäure und/oder Methacrylsäure und 0 bis 10 Gew.-% Acrylamide und/oder Methacylamide und/oder Acrylnitril und/oder Hydroxyalkylmethacrylate, wobei die Komponenten a) und b) zusammen 100 Gew.-% der polymerisierbaren Bestandteile der Mischung ergeben.

The dispersions according to the invention comprise one or more poly (meth) acrylates which have one or more compounds of the formula (I) as comonomer building blocks. These poly (meth) acrylates are preferably obtainable by emulsion polymerization. In detail, the poly (meth) acrylates used according to the invention are composed as follows:

• a) from 0.5 to 25.0 percent by weight of at least one compound of the general formula (I), preferably of a benzophenone (meth) acrylate,
  
  wherein R ^{1 is} hydrogen or methyl, preferably methyl; R ^{2 is} oxygen; R ^{3 is} a radical of the general formula II
  
  wherein R ⁷ , R ⁸ , R ^{9 are} independently hydrogen or methyl, n is an integer from zero to two hundred, o and p are independently an integer from zero to two, in which case the sum of n and o and p are zero, R ^{3 is} a bond; R ^{4 is} a bond, oxygen or O-CO-C, preferably a bond; R ^{5 is} hydrogen, halogen or a moiety having from one to twenty carbon atoms optionally substituted with oxygen, nitrogen and / or sulfur, m being an integer from one to four; and R ^{6 is} an aryl or heterocyclyl radical, preferably a phenyl radical; and
• b) a mixture of further compounds consisting of 40.0 to 99.5% by weight of unfunctional acrylates other than a) 0 to 59.5% by weight of non-functional methacrylates other than a), and / or styrene, 0 to 5.0% by weight of acrylic acid and / or methacrylic acid and 0 to 10% by weight of acrylamides and / or methacylamides and / or acrylonitrile and / or hydroxyalkyl methacrylates, wherein the components a) and b) together 100% by weight of the polymerizable components of the mixture.

Preferably, all of R ⁵ are hydrogen. Also preferably, p, o and n are all zero.

Such a composition, in a manner which can not easily be foreseen, incorporating polymer-bound UV-curable (meth) acrylate polymers in acrylate dispersions known per se, permits the creation of coatings or coatings on textiles or nonwovens with advantageous properties.

Advantage of the system in the coating and / or impregnation of textile fabrics with compositions of the invention is also that neither additional photoinitiators for UV curing are needed nor is expected to migrate the UV-active part, since the UV-active Substance is incorporated as a copolymerized monomer in the corresponding coating.

A very particular advantage, in particular for applications on textiles or nonwovens, is the curing without release of a low molecular weight compound, for example formaldehyde in the prior art. Thus, the inventive method over the prior art in terms of ecological and toxicological aspects of great advantage.

The processing of the dispersions of the invention for the impregnation and / or coating of textiles or nonwovens is composed of applying the aqueous dispersion to the textile fabric, then drying and an adjoining, mostly continuous in a belt plant UV curing. Preferably, in the case of a coating, between drying and UV curing is waited until the film formation of the coating is completed. This usually takes only a few seconds. The application can be carried out by brushing, roller application, printing, spraying, impregnating or padding, preferably by padding. The padding in turn consists at least of the process steps impregnation of the material (textile or nonwoven fabric) in the dispersion and squeezing on rollers.

In the processing of textiles and / or nonwovens, the process according to the invention with UV curing in comparison with thermal curing according to the prior art is advantageous in many respects. On the one hand, the energy consumption is significantly lower, on the other hand, the systems required for padding and subsequent curing can be planned much less space and technically less expensive. A much more protracted thermal curing naturally requires more space than a short UV curing unit.

In addition, it can be observed when using the method according to the invention that the dispersions of the invention are much less prone to coagulation, than the dispersions of the prior art. In addition, the materials show better shear stability and thus better, potentially faster processing.

It is further noteworthy that the benzophenone-containing compounds present in the composition according to the invention are primarily monomers which cure in dispersions by UV crosslinking, and not polymeric photoinitiators. This represents a significant difference from the known prior art.

worin R¹ und R⁵ und sowie m die bereits bei den Formeln (I) angegebenen Bedeutungen besitzen. Die Bedeutung von R¹⁰ ist analog zu der von R⁵, die von q analog zu der von m. Ganz besonders zweckmäßig wird als Komponente a) zur Erzeugung des Polymers für die erfindungsgemäße Zusammensetzung das Benzophenonmethacrylat eingesetzt.A particularly preferred embodiment of the invention is directed to those processes in which compounds a) which correspond to the general formula (J) are used as compounds a). This is the monomer a) at least one benzophenone (meth) acrylate of the general formula (J)

wherein R ¹ and R ⁵ and m and m have the meanings already given for the formulas (I). The meaning of R ¹⁰ is analogous to that of R ⁵ , which of q is analogous to that of m. The benzophenone methacrylate is used particularly expediently as component a) for the production of the polymer for the composition according to the invention.

The compounds of formulas (I) and (J) are either commercially available or are prepared by literature methods. Examples of possible methods of preparation include the transesterification of (meth) acrylates with the corresponding alcohols.

The monomer composition of the benzophenone-containing polymer further comprises one or more ethylenically-unsaturated comonomers b) which can be copolymerized with, but different from, a). The proportion of comonomers is preferably in the range of 75.0 to 99.5 wt .-%. The components a) and b) together give 100 wt .-% of the polymerizable components of the mixture.

In particular, the comonomers b) consisted of the following constituents:
From 40 to 99.5% by weight, preferably from 50 to 98% by weight, of unfunctional acrylates which are different from a),
From 0 to 59.5% by weight, preferably from 0 to 40% by weight, of unfunctional methacrylates which are different from a) and / or styrenes,
0 to 5 wt .-%, preferably 1 to 3 wt .-% acrylic acid and / or methacrylic acid
0 to 15 wt .-%, preferably 0 to 10 wt .-%, particularly preferably 0 wt .-% of acrylamides and / or methacylamides and / or acrylonitrile and / or hydroxyalkyl methacrylates, preferably acrylonitrile.

Acrylates are understood here to mean all functionalized or nonfunctionalized acrylates which are different from a). Preference is given to non-functionalized alkyl acrylates. Particularly preferred are ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate or mixtures of these acrylates.

Methacrylates are understood here to mean all functionalized or non-functionalized methacrylates which are different from a). Preference is given to non-functionalized methalalkyl acrylates. Particularly preferred are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate or mixtures of these methacrylates.

Styrenes are styrene or substituted styrenes, such as. As α-methylstyrene or α-ethylstyrene, preferably unsubstituted styrene understood.

Among hydroxyalkyl (meth) acrylates are (meth) acrylates having a hydroxy group such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 , 5-dimethyl-1,6-hexanediol (meth) acrylate, 1,10-decanediol (meth) acrylate understood.

The monomer composition b) is preferably selected such that the (meth) acrylate polymers used according to the invention have a glass transition temperature of less than 15 ° C., preferably less than 5 ° C. and more preferably less than 0 ° C.

The polymers contained in the dispersions used according to the invention are generally obtained by free-radical polymerization. The usual free radical polymerization is, inter alia, in Ullmanns' Encyclopedia of Industrial Chemistry, Sixth Edition described in detail.

In the present invention, the polymerization is started by using at least one polymerization initiator for the radical polymerization. These include, among others, the well-known in the art azo initiators or organic peroxides.

The polymers according to the invention can be obtained in bulk or else in solution, but the emulsion polymerization is preferred.

The polymerization can be carried out either in the presence or absence of a chain transfer agent. Preferably, the polymerization is carried out in the presence of a chain transfer agent or so-called regulator. As chain transfer agents, typical species described for radical polymerizations can be used. Preference is given to using mercaptans. These are used in a preferred embodiment in an amount of 0.05 to 5 wt .-%, based on the total mass of components a) and b).

The molecular weight of the benzophenone (meth) acrylate-containing copolymers can vary over a wide range. In the context of the present invention, the amounts of monomers, polymerization initiator, chain transfer agent and, if appropriate, solvent are preferably chosen such that a weight average molecular weight in the range from 10 ^{3 to} 10 ⁶ g / mol, preferably in the range from 10 ⁴ to less than 10 ⁶ g / mol, expediently in the range of 2 × 10 ⁴ to less than 10 ⁶ g / mol, in particular in the range of 5 × 10 ⁴ to less than 10 ⁶ g / mol. Particular preference is given to molecular weights in the range from 10 ⁵ to 10 ⁶ g / mol. These values are each based on the weight-average molecular weight (Mw).

The molecular weights can be determined by known methods. Preferably, gel permeation chromatography (GPC), also known as size exclusion chromatography (SEC), is used. It should preferably be measured against polymethylacrylate or polystyrene standards, preferably against a polystyrene standard.

The polymerization to obtain the polymers according to the invention can be carried out at atmospheric pressure, underpressure or overpressure. The polymerization temperature is not critical. In general, however, it is in the range of -20 ° -200 ° C, preferably in the range of 0 ° -180 ° C, favorably in the range of 50 ° -180 ° C, particularly preferably in the range of 50 ° -130 ° C, and in particular in the range of 60 ° -120 ° C.

The compositions are particularly suitable in the form of aqueous dispersions for the production of coatings, coatings and impregnations, in particular for textiles or nonwovens.

The water contained in the aqueous dispersion is in the coating of textiles or nonwovens z. This is not a problem, for example, with regard to rapid drying. In addition, washing after coating the fibers is very likely.

The optionally dried or predried coatings or impregnations can then be crosslinked by irradiation with UV light to give well-adhering coatings which have a high cohesion and a good peel strength with excellent aging resistance. It does not need to be irradiated under inert gas atmosphere, but you can work in the air. As a UV lamp, the usual radiator z. B. mercury vapor low, medium and high pressure lamps are used, the benefits of z. B. 80 to 160 watts / cm can have. Higher power lamps generally allow faster networking. In some cases, in the case of crosslinking radiation, residual solvent or water can be removed simultaneously by the IR component of the lamps.

The coating or impregnation of textiles or nonwovens can have various application-specific advantages. On the one hand, the surface properties of the textile or nonwoven z. B. changed in terms of moisture absorbency or haptics. In addition, a solidification of the textile fabric is effected. A coating can also simultaneously serve as a binder for pigments for coloring. Also possible is the application as an adhesive for flocking.

Examples

The following examples and comparative examples serve to further illustrate the invention without serving to limit it in any way. Above all, the examples show that the dispersions used in the process according to the invention, and thus the process according to the invention, are at least equivalent in comparison with the prior art with regard to the material properties of the end product. In particular, the advantages in terms of apparatus based on UV crosslinking and the toxicological and ecological advantages of the present invention have already been comprehensively set out.

Preparation of the emulsion polymers

All emulsion polymers were prepared by the feed process.

Examples 1-2

First, in a PE beaker, butyl acrylate (BA), methyl methacrylate (MMA), methacryloyloxybenzophenone, methacrylic acid (MAS) (amounts of the monomers are shown in Table 1), 3.0 g ammonium peroxodisulfate (APS), 6.67 g Disponil FES 32 (30%) and water (amount, see Table 1) are emulsified by Ultra-Turrax at 4000 rpm for 3 minutes.

In a 2L glass reactor, which can be tempered with a water bath and was equipped with a paddle stirrer, 390 g of water and 0.833 g of Disponil FES 32 (30%) were initially charged, heated to 80 ° C and with 0.75 g of ammonium peroxodisulfate ( APS), dissolved in 10 g of water, added. 5 minutes after the APS addition, the previously prepared emulsion was dosed within 240 minutes.

After the end of the feed was stirred at 80 ° C and 1 h at 50 ° C for 1 h. It was then cooled to room temperature and the dispersion was filtered through VA mesh with 0.09 mm mesh size. After the end of the feed was neutralized with 2.2 g of 25% ammonia solution and nachstabilisiert with 42.86 g of 70% aqueous Triton X 305 solution. The final neutralization was carried out with 5.8 g of 25% ammonia solution. Table 1 template BA MMA methacryloyloxybenzophenone MAS water Example 2 570.0 g 390.0 g 34.06 g 10.0 g 615.23 g Example 3 570.0 g 360.0 g 68.12 g 10.0 g 616.57 g

The emulsion prepared from Example 1 had a solids content of 49.8% by weight, a pH of 7.65, a viscosity of 125 mPas and an r _N5 value of 67 nm.

The emulsion prepared from Example 2 had a solids content of 49.7% by weight, a pH of 7.75, a viscosity of 159 mPas and an r _N5 value of 65 nm.

The particle radius was determined by PCS (Photon Correlation Spectroscopy), the data given refer to the r50 value (50% of the particles are smaller, 50% are larger). For this purpose, a Beckman Coulter N5 Submicron Particle Size Analyzer was used.

Comparative Examples 1

540.0 g of butyl acrylate (BA), 410.0 g of methyl methacrylate (MMA), 50.85 g of N-methylolmethacrylamide, 10.0 g of methacrylamide, 10.0 g of methacrylic acid (MAS), 3, were initially used in a PE beaker. 0 g of ammonium peroxodisulfate (APS), 16.67 g of Disponil FES 32 (30%) and 585.28 g of water were emulsified by Ultra-Turrax at 4000 rpm for 3 minutes.

In a 2L glass reactor, which can be tempered with a water bath and equipped with a paddle stirrer, 390 g of water and 0.75 g of Disponil FES 32 (30%) were introduced, heated to 80 ° C and 0.75 g Ammonium peroxodisulfate (APS), dissolved in 10 g of water. 5 minutes after the APS addition, the previously prepared emulsion was dosed within 240 minutes.

After the end of the feed was stirred at 80 ° C and 1 h at 50 ° C for 1 h. It was then cooled to room temperature and the dispersion was filtered through VA mesh with 0.09 mm mesh size. After the end of the feed was nachstabilisiert with 19.04 g of 70% aqueous Triton X 305 solution.

The emulsion prepared from Comparative Example 1 had a solids content of 49.4% by weight, a pH of 2.7, a viscosity of 62.5 mPas and an r _N5 value of 67 nm.

polyester fleece

The further investigations were carried out on a polyester fleece 70/30 PES (1.7 / 3.3 dtex) from Gebr. Röders AG. This polyester fleece has a basis weight of 50 g / m ² and has the following stabilization: pre-needled with 25 stitches / cm, 15 mm deep with needles 36 R.

sample preparation

Nonwoven material measuring 25 cm x 30 cm with sewn edge areas was used. The edge areas were sewn off to reduce deformation. The nonwoven fabric was immersed over a period of 5 minutes in the corresponding dispersion, padded and dried depending on the dispersion used either in a drying oven for 5 min at 140 ° C (comparative example) or by UV irradiation (Examples 1 and 2). Before the irradiation, the samples equipped with the example dispersions were heated in a drying oven at 80 ° C. for 5 minutes. For light-induced solidification, a UV irradiation system with linear power control and continuous material guidance from Printconcept using a Hg broadband radiator with the following characteristics was used:
Maximum intensity: 365 nm
Maximum power: 160 W / cm
Lamp width: 30 cm

Double measurements were carried out with two samples each.

• – Gravimetrische Bestimmung des aufgebrachten Binderanteils (jeweils 14 Messungen). Die Angaben der Gewichtszunahme erfolgt prozentual bezogen auf das Gewicht des trockenen Vlieses.
• – Kochwäsche mit gravimetrischer Bestimmung des Gewichtsverlusts in Vierfachbestimmung. Die Probe wird ausgewogen (T₁) und in 150 mL einer wässrigen Lösung, die 3,3 g Seife (Marseiller Seife) und 2,2 g kalciniertes Soda enthält, 10 min. bei 90° im Linitestgerät behandelt Anschließend wird das Gewebe einmal mit 90°C heißem und einmal mit kaltem Wasser (jeweils ca. 100 mL) gespült und 30 min bei 80°C getrocknet. Nach halbstündigem Liegen bei Raumtemperatur wird ausgewogen (T₂). Der Gewichtsverlust ist die Differenz zwischen T₁ und T₂. Die Differenz wird prozentual, bezogen auf das Gewicht T₁ des behandelten Gewebestreifens angegeben.
• – Tri-Wäsche mit 1,1,2-Trichlorethylen mit gravimetrischer Bestimmung des Gewichtsverlusts in Vierfachbestimmung. Die Probe wird ausgewogen (T₁) und in 150 mL Trichloräthylen 20 min. bei 20° im Linitestgerät behandelt Anschließend wird das Gewebe in 100 mL reinem Trichloräthylen gespült und 30 min bei 80°C getrocknet. Nach halbstündigem Liegen bei Raumtemperatur wird ausgewogen (T₂). Der Triwaschverlust ist die Differenz zwischen T₁ und T₂. Die Differenz wird prozentual, bezogen auf das Gewicht T₁ des behandelten Gewebestreifens angegeben.
• – Zugprüfung mit einer Zweigle nach DIN EN 29073-3 mit folgenden Prüfbedingungen: 200 mm Einspannlänge; 50 mm Breite; 5 cN Vorspannung; 100 mm/min Geschwindigkeit; 20 mm/min Geschwindigkeit bis Vorspannung; 99% Kraftabfall
• – Bestimmung der Biege- und Kompressionseigenschaften mittels Kawabata-Messung mit Probenabmessung 20 cm·20 cm; Die Biegeprüfung wurde mit 20 cm langen und 2 cm breiten Streifen nur in Längsrichtung durchgeführt.

In addition, the following measurements were also performed at least in duplicate:

• - Gravimetric determination of the applied binder content (14 measurements each). The details of the weight gain is based on the percentage of the weight of the dry web.
• - Cooking wash with gravimetric determination of weight loss in quadruplicate. The sample is weighed out (T ₁ ) and dissolved in 150 mL of an aqueous solution containing 3.3 g of soap (Marseille soap) and 2.2 g of calcined soda for 10 min. The tissue is then rinsed once with 90 ° C. and once with cold water (in each case approx. 100 ml) and dried at 80 ° C. for 30 min. After half an hour lying at room temperature is balanced (T ₂ ). The weight loss is the difference between T ₁ and T ₂ . The difference is expressed in percent, based on the weight T _{1 of} the treated tissue strip.
• Tri-wash with 1,1,2-trichlorethylene with gravimetric determination of weight loss in quadruplicate. The sample is weighed out (T ₁ ) and in 150 mL trichlorethylene for 20 min. The tissue is then rinsed in 100 ml of pure trichlorethylene and dried at 80 ° C. for 30 minutes. After half an hour lying at room temperature is balanced (T ₂ ). The trash loss is the difference between T ₁ and T ₂ . The difference is expressed in percent, based on the weight T _{1 of} the treated tissue strip.
• - Train test with a Zweigle after DIN EN 29073-3 with the following test conditions: 200 mm clamping length; 50 mm wide; 5 cN bias voltage; 100 mm / min speed; 20 mm / min speed to preload; 99% power loss
• - Determination of the bending and compression properties by Kawabata measurement with sample size 20 cm x 20 cm; The bending test was carried out with 20 cm long and 2 cm wide strips only in the longitudinal direction.

All percentages in the following tables are percentages by weight unless otherwise stated. Table 2: Proportion of the binder on different non-woven samples fleece Comparative Example 1 example 1 Example 2 1 102.9% 88.9% 99.6% 2 93.7% 87.7% 98.9% 3 96.9% 84.9% 96.7% 4 105.5% 95.7% 94.4% 5 102.8% 79.3% 92.3% 6 98.3% 77.5% 91.8% 7 87.1% 76.9% 86.8% 8th 101.3% 81.4% 86.6% 9 103.6% 86.8% 80.3% 10 149.8% 88.4% 85.0% 11 86.7% 93.3% 91.6% 12 98.6% 93.3% 86.7% 13 105.1% 98.2% 96.3% 14 132.0% 104.5% 90.7% average 105.3% 88.3% 91.3%

The binder content of the comparative example according to the prior art is slightly higher than the proportion of the inventive examples. However, this result is not very significant in terms of the values. Table 3: Gravimetrically determined weight change after cooking fleece Comparative Example 1 example 1 Example 2 1 + 0.5% -0.4% -0.2% 2 + 0.2% -0.4% -0.2% 3 + 0.8% -0.4% -0.3% 4 + 0.7% -0.5% -0.5% average + 0.5% -0.4% -0.3% Table 4 Gravimetrically determined weight change after tri-wash fleece Comparative Example 1 example 1 Example 2 5 -0.5% -4.2% -3.1% 6 -0.8% -2.7% -3.8% 7 -0.9% -3.6% -2.6% 8th -1.2% -2.5% -3.5% average -0.8% -3.2% -3.1%

It can be seen from the results of Tables 3 and 4 that the weight losses in the web stabilization carried out according to the invention are slightly higher than in the case of the corresponding equipment with the dispersion according to the prior art. The weight gain of the results of the comparative example in Table 3 is due to absorbed water.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 4511699 [0003]
• GB 1411268 [0003]
• EP 0355028 A1 [0004, 0005, 0006]
• US 5900472 A [0009, 0009]
• WO 2002100912 [0010]
• DE 1720603 [0011]
• DE 1720605 [0011, 0011]

Cited non-patent literature

• Carlini et al. Report in Polymer, 1983, Vol. 24, May, page 599 et seq. [0008]
• Ullmanns' Encyclopedia of Industrial Chemistry, Sixth Edition [0039]
• DIN EN 29073-3 [0065]

Claims (10)

Use of an aqueous dispersion for coating and / or impregnating textiles or nonwovens, characterized in that the dispersion comprises one or a plurality of (meth) acrylate polymers which comprise one or a plurality of the compounds of the general formula (I) in copolymerized form and which are obtainable by emulsion polymerization of a mixture comprising a) from 0.5 to 25.0 percent by weight of at least one compound of the general formula (I)

wherein R ^{1 is} hydrogen or methyl; R ^{2 is} oxygen; R ^{3 is} a radical of the general formula II

wherein R ⁷ , R ⁸ , R ^{9 are} independently hydrogen or methyl, n is an integer from zero to two hundred, o and p are independently an integer from zero to two, in which case the sum of n and o and p are zero, R ^{3 is} a bond; R ^{4 is} a bond, oxygen or O-CO-O; R ^{5 is} hydrogen, halogen or a moiety having from one to twenty carbon atoms optionally substituted with oxygen, nitrogen and / or sulfur, where m is an integer from one to five; and R ^{6 is} an aryl or heterocyclyl radical; and b) a mixture of further compounds consisting of from 40.0 to 99.5% by weight of unfunctional acrylates other than a) from 0 to 59.5% by weight of unfunctional methacrylates other than a), and / or styrene, 0 to 5.0% by weight of acrylic acid and / or methacrylic acid and 0 to 10% by weight of acrylamides and / or methacylamides and / or acrylonitrile and / or hydroxyalkyl methacrylates, wherein the components a) and b) together 100% by weight of the polymerizable components of the mixture. Use of a dispersion according to claim 1, characterized in that R ^{1 is} methyl, that R ^{2 is} oxygen, that all R ^{5 are} hydrogen, that R ^{4 is} a bond, that R ^{6 is} phenyl, and that p = o = n = Zero. Use of a dispersion according to Claim 1, characterized in that the acrylates of mixture b) are ethyl acrylate, propyl acrylate, butyl acrylate or ethylhexyl acrylate or mixtures of these acrylates. Use of a dispersion according to Claim 1, characterized in that the methacrylates of mixture b) are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate or mixtures of these methacrylates. Use of a dispersion according to Claim 1, characterized in that the (meth) acrylate polymers have a glass transition temperature of less than 5 ° C. Use of a dispersion according to at least one of claims 1 to 5, characterized in that the (meth) acrylate polymers are composed of 1.0 to 10.0 wt .-% of the compound a), 50.0 bis 98.0% by weight of acrylates, 0 to 40.0% by weight of methacrylates and 1.0 to 3.0% by weight of acrylic acid and / or methacrylic acid. Use of a dispersion according to one of the preceding claims 1 to 6 for the coating and / or impregnation of textiles or nonwovens, characterized in that the coating and / or impregnation is carried out by application, subsequent drying and subsequent curing by means of UV radiation. Use of a dispersion according to claim 7, characterized in that the application is a brushing, a roller application, printing, spraying, impregnating or padding, preferably padding. Textile surface fabric, characterized in that it is coated or impregnated with a benzophenone-functional polymethacrylate. A textile fabric according to claim 9, characterized in that the textile fabric is a textile, a fabric, a cloth, a woven fabric, a knitted fabric, a knitted fabric, a nonwoven fabric, a nonwoven fabric, a cotton wool or a felt.