DE1494860A1 - Process for coating fibers, in particular mineral fibers such as glass fibers - Google Patents

Description

Dr.-Ir.g. Heinrich Scheller

Patent attorney

AACHEN, Zollernstr. ] Tel _e fon: 3 2192 and 25182

Aachen, March 4th, 1966 My reference PaGm 11 660

Aachen-Gerresneimer Textilglas GmbH. - Gevetex, Aachen

Priority from the French patent application fir. 46 761 of January 21, 1966

Process for coating fibers, in particular mineral fibers such as glass fibers

The invention relates to a coating method of fibers, especially mineral fibers such as glass fibers, to improve processability and the appearance as well as to improve the processing

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availability of a product made from such fibers in the form of rovings, mats, cut fiberglass, fabrics and the like with plastics. ■

In contrast to most other fibers, glass fibers are sensitive to abrasion and will be destroyed if they do their surfaces are not protected against this. So it is important to provide them with a coating, which adheres firmly to their surface and gives them the desired processing properties that their further processing into rovings, mats, cut fiberglass, fabrics and the like. As well as their use for Enable the production of reinforced plastics.

As a reinforcement and as a means to increase flexibility • glass fibers are already used together with synthetic resins for the production of glass fiber reinforced plastics, laminates and coated fabrics used. In the manufacture of such bodies one must have a firm bond between the smooth glass surfaces and the resin to be reinforced by the glass fiber. This bond must be temperature, water and chemical resistant and have good aging resistance.

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Glass fibers are not porous, nor do they have a rough surface that allows adequate bonding physical forces would allow. They also have little or no affinity for most Plastics have a hydrophilic character and are therefore susceptible to moisture, so that one on the A film of a size or a resin binder present on the fiber surface under humid conditions can easily be displaced by a film of water »

The glass fibers, however, have extremely good properties in terms of mechanical strength, and efforts are made to to use them for such purposes and in such a way that these properties also come into play If good adhesion between the glass fibers and the plastics is not achieved, the glass fibers can do theirs full effectiveness in terms of improving the strength properties of the products made from them is not unfold

Raise the two basic requirements that a coating or size for the glass fiber must meet, namely Protection against mechanical abrasion and adhesion to the plastic, however, are still a number of other requirements the properties of the sized fiber.

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For the production of bound or unbound mats, the spun thread as such or in the form can be cut from rovings. The distribution of the cut threads should be even, without piling made of fiber bundles and often as a flat fiber fleece. The impregnation and impregnation with resin is intended proceed as quickly as possible and without the formation of too many air bubbles. For many applications, a transparent ^ fiber reinforced plastic part with an only slightly visible fiber structure is desirable changes little even after exposure to moisture, high mechanical strength values are also after weathering he wishes.

The behavior of the glass fiber during processing and in the finished glass fiber reinforced plastic part is decisive determined by the composition of the size with which the thread is treated. Some of these demands have not yet been satisfactorily fulfilled; So it turned out, for example, that for the cutting process in general one hard thread is required, while a soft "open" thread is more advantageous for better impregnation with resin and leads to better laminate transparency under certain conditions. When cutting spinning or Roving threads must take into account the electrostatic charge

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which makes it difficult to evenly distribute the fibers, and practical work is impossible can make. Charging occurs particularly easily when Cutting hard threads.

The size is used during the manufacture of the elementary glass fibers applied to these prior to their union to form the spun thread and contains, provided that the glass fibers with synthetic I to be processed resin, in addition to a film former, optionally with plasticizer and lubricant, also a Adhesive.

The size is usually used as the film former Polymers such as polyvinyl acetate (cf. German patent specification

1 010 491) »polyacrylate and the like are used, or, for example, polyester (see German patent specification 1 005 464) or Epoxy resin "(cf. French patents 1,389,707 j and 1 392 083)

Organic chromium compounds, for example, serve as bonding agents » such as chromium chloride methacrylate or organic silicon compounds, such as vinyltriehlorosilane (see German Patent Specification 1 010 491) or methacrylsilane.

It has also been proposed (see US Pat

2 958 812), the improvement of the processability and the

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To bring about affinity of the glass fibers to synthetic resins by a treatment of the glass fibers, by the on these a complex compound of a titanium ester with an organic compound from the amine, Alcohols and hydroxyamines comprehensive group is produced.

None of the previously known sizes listed above allows a spun thread to be produced which is Can be processed and cut well and can also be impregnated with resin in a very short time, in particular Polyester resin, guaranteed.

Also, it has so far only been insufficiently possible to produce a jade that was not sticky, dusty and fluffy, sufficiently supple and abrasion-resistant to withstand all textile operations such as camouflaging, twisting, weaving, etc. without damage .

The invention is based on the object of eliminating the disadvantages described above and of producing a thread which meets all the requirements placed on it.

To achieve this object, the method according to the invention for coating fibers, in particular of

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mineral fibers such as glass fibers, in which these with a polymer or a copolymer of an ethylene, ester- or epoxy-containing compound and organosilane, optionally also containing plasticizers Solution or dispersion coated, combined to form threads and dried, characterized in that the treatment of the fibers with a solution or an aqueous dispersion of such a polymer or Copolymer is made in which an organic titanium compound, preferably a tetraorgano derivative of orthotitanic acid together with at least one Organo-silane from the unsaturated silanes, epoxydsilanes or aminosilanes comprehensive group are included.

It has been found that by the method according to the invention dung a hard thread is obtained that meets all requirements for a proper cutting process, anyway has no disruptive electrostatic charge and at the same time shows impregnation properties in the resin, as it does were previously not achievable for a thread capable of cutting.

In addition, the laminates made therefrom, for example polyester resin, show an obvious improvement in terms of their transparency and that of the

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The fiber image present on the laminate surface becomes less visible. A noticeable fiber structure is not only undesirable for optical reasons, e.g. due to the increased clouding of the glass fiber reinforced plastic panels when exposed to moisture, but it can also lead to unfavorable mechanical properties when exposed to weathering to lead.

In contrast, the laminates produced according to the invention also have improved mechanical strength properties which express themselves in particular in an increased rigidity, which is important for the aging behavior of laminates is important. The size and adhesive combination according to the invention thus has an increased effect Adhesion to the glass-resin interface. This combination of sizes is such that it is possible is to achieve a further increase in strength by adding the same or a different adhesive to the resin. In this way, for example, mechanical dry and wet strength values can be achieved with standard polyester resins, as they have not yet become known for these resins and which approach values for epoxy resins β

The well-bound thread also has improved running properties, which is important for the production and processing>'-!' 1 '''-i'i:j': eu v: i. <* Ut: <_, is. Kaon dem ^ n iriduntP ^ ciiiäbtT. V ■ -r-

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It is also possible to process spun threads that are made up of several loosely interconnected partial threads order, e.g. 3. from four partial threads and more.

Such threads can also be processed on cutting units, which work on the principle of kinking or shearing and, in contrast to the threads J with the so far known sizes, even when sheared, an only slightly voluminous structure made from perfect cut, non-sticking threads with a smooth, "calm" surface. The volume of such Unbound matting or fiber webs is also available when using of spun threads low, if these consist of four partial threads and more · Favor the flat structures obtained a faster soaking with resin, prevent air » Inclusive and unwanted shifting (floating out) the loose mat after the end of the soaking period in the trough * - zone, * .B. by placing a film *

The threads sized according to the process according to the invention can, as usual, by a drying process at temperatures between 80 ° and. 160 ⁰ C dry. The drying time can be shortened by high-frequency drying without, in contrast to the usual sizes, the thread hardness becoming too low.

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The inventive method also improves - at Use for finishing - the workability of the Fibers in the production of rovings, mats, cut glass silk, yarns, twisted threads, woven fabrics and the like.

The method according to the invention can be used both for sizing in the manufacture of the glass fibers, as well as

for the original size after the removal ax be used for dressing the threads before the threads are further processed into a fabric, or directly to the finishing of the fabric.

According to the invention, use can be found as film formers Polymer · and copolymers of vinyl acetate ^ Acrylic and methacrylic acid esters, vinyl chloride, styrene, butadiene, acrylonitrile, chlorovinyl acetate, vinylidene chloride. In addition, they are suitable as a file generator according to the invention saturated © polyester, manufactured s.B. "Do succinic" and phthalic anhydride and propylene glycol, polycarbonates or unsaturated polyesters based on maleic or Fumaric acid, furthermore epoxy resins e.g. cycloaliphatic diepoxides or epoxies based on BaS ia bisphenol A, if necessary with hardeners such as amines, acid anhydrides and especially amino fatty acid amides.

Many of these film formers, which lead to a soft, sticky sizing film, are

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the titanate compound according to the invention is harder and can largely lose their stickiness, so that the sized thread is easier to process.

The unsaturated silanes preferred according to the invention are methacrylsilane, such as gamma-methacryloxypropyltrimethoxysilane, and vinylsilane, such as Vinyltrimethoxyäthoa ^ · silane. But there are also epoxysilanes, such as

3,4- epoxycyclohexylethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, also amino-silanes, such as gamma-aminopropyltriethoxysilane as well as diaminosilanes into consideration.

To further reduce the inherently low electrostatic charge, chlorosilanes such as Vinyltrichlorosilane, vinyldichloralkoxysilane, vinylchlorodialkoxysilane, but also chromium complexes such as chromium chloride methacrylate are also used in smaller quantities will.

The organic titanium derivatives preferred according to the invention are titanium esters or titanium chelates, e.g. octylene glycol titanate, titanium acetonyiacetonate, butyl titanate, propyl titanate, Isopropyl titanate, 2-ithyl hexyl titanate, titanium lactate, Triethanolamine titanate, oleyl titanate, stearyl titanate, Vinyl, allyl titanate »but also derivatives that by reacting a titanium ester with saturated or unsaturated Alcohols and / or capable of enol formation

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Connections are obtained. The molar ratio between titanate and alcohol or enol can be within limits 10: 1 or 1: 4, e.g. between 1 mole of tetraisopropyl titanate and 0.1-4 moles, preferably 0.8-3 moles Acetylacetone or acetoacetic ester. All such compounds can be in monomeric or polymeric form or in the form of titanium compounds mixed with one another

When working in the aqueous phase, good stability is essential to pay attention to the solution or the dispersion, which is increased by a suitable pH adjustment. In the case of Tit an-Ac et ony Iac et onat are commonly acids, such as acetic acid or hydrochloric acid is used. Here, however, an addition of lower alcohols such as Isopropyl alcohol, necessary. Such solvents work often disadvantageous. When sizing the resulting threads below the hot nozzle, they are unpleasant odor and flammable and can use the plastic and others

by loosening / attacking parts of the sizing system, sources, etc.

It has been found that the addition of compounds containing hydroxyl groups, e.g., oxy acids such as glycolic acid, reduces the solvent content reduced if necessary gear can be omitted. The stability of the size dispersion is increased further and prevents subsequent precipitation of size constituents. Furthermore, one achieves through the content of

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Oxy acids that the resulting film is coherent and

Sch / is closed more tightly, making the ^ fire resistance

the threads treated with it is increased.

According to the invention, the size can also contain a plasticizer such as that for polyvinyl acetate or Polyvinyl chloride is known, e.g. from the group of phthalates, phosphates, adipates, sebacates or Oxycarboxylic acid esters, epoxy plasticizers such as epoxidized glycerides or alkyl epoxystearates.

It was surprisingly found that in particular plasticizers based on esters, such as dibutyl phthalate, Does not soften in the presence of the titanium compounds act, but on the contrary lead to a harder thread without the flexibilizing effect of the soft mac riers is lost.

Cationaküive compounds can be used as ürleit- and wetting agents can be used, e.g. oäureamides which are smeared soluble with acids, such as pelargonic acid amides, alkylimidazoline derivatives, Fatty acid amides of polyamines, such as tetraethylene pentamine, but also quaternary alkylammonium compounds such as trimetijylötearylummoniumchlorid, also fatty acid amines in Form of their salts, such as acetic acid or methacrylic acid.

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Nonionic wetting agents can also be used alone or in combination with the cationic lubricants will. These include polyglycols, also with a molecular weight of e.g. 20,000 and higher, as well Polyglycols obtained by block polymerization of

Polypropylene glycol can be obtained with polyethylene oxide or vice versa, ethylene oxide and propylene oxide condensates with fatty acids, fatty alcohols, alkylphenols. Such Products cause an additional wetting and stabilizing effect of the aqueous size dispersion, but which is reduced after the drying process by the presence of the organic titanium compounds, and thus the water resistance of the sized fibers is increased. As an added benefit is the further reduction the electrostatic charge can be seen with a small addition. In addition to these notiagenen can other compounds containing hydroxyl groups, such as fatty alcohols, phenols, can also be used «

The use of these products in a proportion of -2-50 percent by weight, based on the titanium compound.

The glass fibers treated by the process according to the invention are also particularly suitable for the production of Mats pre-impregnated with polyester resin, fiber strips, cut Glasf3e1.de uüw .. When adding alkaline earth

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oxides or salts to the polyester resin to obtain a faster and stronger drying impregnation material · Ee groups may also be flame-resistant, elastic and other types of resins are also used.

For the textile processing of the thread, such as for yarn, twisting, plying, weaving, the thread should be well bound, | non- sticky, dusty and fluffy, sufficiently supple and abrasion-resistant and have the lowest possible electrostatic charge in order to be able to withstand all textile work processes without damage. In USAGE dung Röa a "such a thread for plastic reinforcement the demand for a stable liability TOXI glass Sn is additionally the particular polymer into consideration.

Of the film formers which can be used according to the invention, polyester resins, polycarbonates and epoxy resins, alone or in combination with curing agent, are particularly suitable for this purpose. As such a crosslinking agent, in particular Aminofettsäureamide are suitable which persion in aqueous Dis curing act on the Epoxdharze and at the same time in an acidic medium represent emulsifiers for this. By the appropriate choice of epoxy resin and hardener xkxkjsxkx a softer, harder geschmeidigerer or thread can be with the use of equimolar amounts of curing agent based on the epoxy equivalent obtained. As beneficial

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have shown crosslinking substances such as amino fatty acid amides in an amount of 0.1 to 2 mol, preferably 0.4-1.5 mol, based on the epoxy equivalent of the resin. The addition of an organic titanium compound according to the invention causes a considerable reduction in the liquid, which has a disruptive effect in the production of yarns, twisted threads, and ply material and makes further processing, e.g. into fabrics, more difficult. This expresses itself in the * surprisingly high tear strength of from 9 / u existing filaments spun yarn from which _t or after the processing for yarn twisting a mean of

ρ
160 kp / mm and more achieved.

Such strength values are not achieved by a commercially available spun thread made of ueentary threads with 9 / U diameter and have so far only been achieved by much finer threads, such as, for example, spun threads made of elementary threads with 5 / u. Been Durcn- _(knife, reached that usually fat combination starch geschlicntet with and therefore are not compatible with plastics "

The surprisingly beneficial effect of the invention Process with regard to the tensile strength of the thread and suitability for textile processing can possibly to the spontaneous generation of a film in situ on the Recirculated fiber from the components of the invention will.

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Under the comparatively mild conditions for sizing and subsequent drying dex * is produced spinning bobbins a complete conversion of the epoxy resin with the hardener is not given, üin a larger excess of hardener, e.g. Amino fatty acid amides, may well promote this, but v / iritt A higher hardener content in this hardener is often disadvantageous due to the free amino groups still present regarding adhesion and water absorption of the reinforced Plastic made of β

By type and amount of the organic contained according to the invention Titanium compounds can be used to influence the degree of crosslinking of the epoxy resin.

In this way, the amount of hardener can optionally be reduced, which can promote water resistance and aging behavior of the reinforcing product. in the In the case of amino fatty acid amides, for example, these compounds act primarily as emulsifiers and only secondly Line as a hardener.

ii & ch the inventive method, it is possible to Fiden, for example, as spinning bobbin to dry as usual, for example wänrend 8 hours at 80 ° - 130 ⁰ O, but also a short time by dielectric drying without the erfindungsgernäßen advantages lost. However, the invention sees

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also offers the possibility of air drying. In this case the drying temperature is relatively low: on the order of 20 ^° C. and the drying time can be 20 hours or more.

To improve the adhesion of the glass fiber to plastic, depending on the plastic used, a special adhesive can be added, e.g. methacrylic and vinyl silane for polyester resins, aminosilanes for epoxy, phenolic, urea and melamine resins, methacrylic silane for polyethylene etc.

with polyester resins. surprisingly turns out aminosilane is often even cheaper than vinyl and iViethacrylsilan. i3ei. Use of aminosilanes as adhesive is thus the method according to the invention both for polyester resins and for epoxy, phenolic, Urea and melamine resins or silicones.

Even if the glass fibers treated by the process according to the invention bring about particularly good properties of the reinforced plastic body during further processing with polyester resins, they are also suitable for processing with other heat-resistant resins such as epoxy resins and thermoplastic resins such as polyvinyl chloride, polyethylene, etc.,. but also for elastomers due to the increased adhesive effect in the combination of silane adhesive and the titaniumfckampleXß. . - p ^ D ORIGINAL

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Although the method according to the invention primarily is intended for glass fibers and in the following also the Application of the method for such is described in detail, the method is also suitable for coating of other fibers of a natural or synthetic nature, especially the fibers treated with them to give better water-repellent properties and a higher abrasion resistance.

^ festJ
The total solids content of the aqueous treatment agent is, according to the invention, about 1-6 percent by weight, of which about 1-5 percent by weight is polymer or copolymer, about 0.1-2.5 percent by weight of organic titanium compound, about 0.05-2 percent by weight of silane , optionally about 0.1-1 weight percent plasticizer and optionally about 0.05-1 weight percent wetting agent.

Below are some examples of sizes according to the invention to be applied to glass fibers, which give them good processing and strength properties, in particular in the case of the later use of the glass fibers together with plastics, especially polyor /, or- and epoxy resins for the purpose of producing resin. is. «. ^v ι, ^1st fabric bodies:

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Plain examples; Example I.

constituents of the size percent by weight

Vinyl trichlorosilane 0.08

Gaiama methacryloxypropyltrimethoxysilane 0.2

Polyvinyl acetate (52 weight percent dry 4.1

substance 'with dibutyl phthalate Titanium acetonylacetonate '1.3

Glycolic Acid (10 ft) ' 0.5

Imidazoline coconut fatty acid condensate 0.08

Fatty alcohol polyglycol ether 0.16

3est V / ater

The sized thread ^ differs markedly from one Thread that has been treated with a size of known composition only with vinylsilane as an adhesive.

The spun thread combined to form a roving strand shows less Loops and fluff that impair proper processing. The thread is harder, tied more tightly and can be cut without difficulty and too untied Process mats, preforms or molded parts that are after The fiber spray process can be obtained. For cutting, 3ich systems based on the principle of shearing, breaking or use pinch off.

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The Hoving strand cut according to the ücher principle leads to a more even fiber distribution, the surface is much smoother, "quieter", the installation height in the range of 2.5 - 4.5 cm is lower and more even opposite 3 - 7 cm of the thread with size only with vinyl silane. The soaking time with a standard polyester resin is 3-4 times shorter than with thread with the comparative slice (measured by the time of soaking an unbound mat as well as the license

■ —ί'ί
permeability in the photometer). The transparency of the light plates is significantly improved, the fiber image is only slightly visible and practically does not deteriorate even when stored in cold water for a week or more.

Also resistance to hot water treatment is good.

Example II

Components by weight

Vinyltrimethoxyethoxysilane ü, 50

Condensation product of pelaric acid

solubilized with a polyamine

with acetic acid 0.25

Polyvinyl acetate dispersion (50% by weight) with Dibut;, ylphthalate

Cctylene glycol titanate remainder water 00984 1 / 0U5 x) dry

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Despite the low concentration of titanate, the hardness of the thread is increased without reducing the transparency is worsened »

100 liters of size can be produced in the following way will:

1) 0.17 l of acetic acid (60 ^c / o) are added to 40 l of water at a maximum of 16 ^° C., and the intended amount of vinyltrimethoxyethoxysilane is slowly added »

2) Pelargonic acid-polyamine condensation product, which with Acetic acid is made water-soluble, is diluted with four times the weight of water of approx. 40 g and to 1) added. The mixture must become clear.

3) Slowly stirring the octylene glycol titanate into the concentrated, 5 % dibutyl phthalate-containing polyvinyl acetate dispersion, careful dilution with stirring with approx. 10 1 water.

4) Stirring the mixture 1) and 2) into the dispersion 3)

5) Adjust the pH to 4.0-4.5 with Ammonia or malt acid.

6) Fill up with water to 100 1st ^{RaD original}

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Example III

Components by weight

Vinyl trimethoxyethoxysilane 0.5

Pelargonic acid amide, soluble with acetic acid

made 0.12

Imidazoline fatty acid condensate 0.05

Polyvinyl acetate (50 percent by weight

Dry matter) 4.8

Titanium acetylacetonate 0.5

Isopropanol 1.3 remainder water

The thread is hard and easy to cut. Despite the higher thread hardness, the transparency is very good

Example IV

Components by weight

Vinyltrichlorosilane 0.1

Gamma-methacryloxypropyltrimethoxysilane 0.2

Fatty alcohol polyglycol ether 0.2

Titanium acetonylacetoriate 1.5

Isopropanol 2.4

Polyvinyl acetate (50 percent by weight
Dry substance) with 20% dibutyl phthalate 4.1 remainder water

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The thread shows in spite of its high length at Weichiaacher a much greater hardness than without plasticizer ge-i.alto Takes place on cutting tools according to the shear principle Case and distribution impeccable. The fiber web is particularly flat (2-3 cm). The impregnation with resin happens very quickly, and the transparency of the polyester resin plate is also after TiVassereinaction, - senr good "

Example V

Components by weight

Vinyltriethoxysilane U, 5

relargonic acid amide, made soluble with

Acetic acid 0.5

Titanium acetylacetonate 0.5

Ainof atty acid aiTide 1.6

polyaminoamide 0.33

Lp oxide nar ζ 0.6

epoxidized triglyceride 1.0

Poly-lycol ■ 0.1

Isopropanol 1.3 kest of water

The thread sized with this approach shows coagulation? Lui; <- nbi l'iung. eη Kj.-in textileii processing for twisting, to, ίΠ [ule and ι eim weaving, UEIC Heißfetiti _t, ness eiüss ZvvMT'ij hcii'.rt 1t ''. ' Kivnirc '". Üiin ^ oiriu' ·· Kudei: ei <net:; i

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especially for textile use, reinforcement of paper and. its coating with a thermoplastic resin.

The invention is not restricted to the exemplary embodiments described in detail above, but rather In contrast, numerous changes are possible without departing from the scope of the invention.

All features that are mentioned in the above description are intended, provided that the known state of the art this allows, on its own or in any combination or partial combination, to be essential to the invention be viewed even if they are not included in the claims

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Claims (12)

U94860 Dr.-Ing. Heinrich Steller Aaohen 'den *' fcl 1966 patent attorney Meinzeichen PaGm 11 660 AACHEN, Zollemstr. 1 phone: 3 2192 and 25182 claims 1) Process for coating fibers, in particular mineral fibers such as glass fibers, in which these with a polymer or copolymer of an ethylene, ester or epoxy-containing compound and organosilane, possibly also plasticizers containing solution or dispersion coated, combined to form a spun thread and dried; are characterized in that the treatment of the fibers made with a solution or an aqueous dispersion of such a polymer or copolymer is, in which an organic titanium compound, preferably a tetraorgano derivative of orthotitanic acid together with at least one organo-oil the unsaturated silanes, epoxy or amino silanes comprehensive group are included 2) Method according to claim 1, characterized in that as unsaturated silicon, a methacrylic silane such as gamma-methacryloxypropyltrimethoxys'ilane is used. 3) Method according to one or both of claims 1 and 2, characterized in that the unsaturated silane is a vinylsilane, such as vinyltrimethoxyethoxysilane or Vinyltrichlorosilane is used. BAD ORfQiNAL 0098A1 / QU5 U94860 - Ts - • η 4) Method according to claim 1, characterized in that that as epoxysilane j5,4 ~ Epoxycycjrflohexyläthyltrimethoxysilan or glicidoxypropyltrimethoxysilane is used. 5) Method according to claim 1, characterized in that that as aminosilane gamma-aminopropyltriethoxysilane is used. 6) Method according to one or more of the preceding claims, characterized by the use of Titanium acetonylacetonate as an organic titanium compound. 7) Method according to one or more of the preceding claims 1 to 5 »characterized in that a Titanium derivative is used, which is obtained by reacting a titanium ester with alcohols or enols, e.g. TetraisopiOpyltitanat is made with 0.1-4 mol, preferably 0.8-3 tool acetylacetone. 8) Method according to claim 6 or 7 »characterized in that that oxy acids such as glycolic acid are used to stabilize the titanium compounds in the aqueous medium. 00984 1 / OU 5 U94860 ZS 9) Method according to one or more of the preceding claims, characterized gekennzeicnnet that epoxy resins with optionally crosslinking substances, such as aminof ettsaureamide in an ivienge of 0.1-2 mol, preferably t $$ -1.3 I "ol, as film formers on the epoxy equivalent of the resin. 10) Proceeding according to one or more of the preceding Claims, characterized in that the size a Weiciunacher, e.g. dibutyl phthalate is added. 11) Method according to one or more of the preceding Claims, characterized in that the light Hydroxyl group carriers such as polyglycols, ethylene oxide condensates of fatty alcohols, fatty acids, alkylphenols are added in simple :. Share of 2-50 percent by weight based on the titanium compound. 12) Verfanrexx ri & cix one or more of the preceding Claims, characterized geAerinzfeicii ^ ei; that the treatment xit takes place with a watery L.eaium, its whirlwind υ off salary, among other things, amounts to 1-6 percent by weight, of which u ^ t'efarj? 1-5 percent by weight polymer or Lliscupolymer, about 0.1-2.5 percent by weight orgeuTiiscr.e titanium compound, ur.-_ efär.r 0.05 - ^ percent by weight Silar. and possibly us ei'iir-r 0.1-1 3ev.icntsprozer-t Vieichaacher and ur ^ efE-ir ü, 05 - 1 Ge BATH ORIGINAL v.ic: .tερΐ ο ^ -r.c ^ 00984 1 / 0U5