NO311728B1 - Antistatic agent, method of manufacture thereof, and use thereof for the manufacture of antistatic coatings - Google Patents

Abstract

Antistatic contains organically modified silicic acid (hetero)polycondensate(s), obtained by hydrolytic (partial) condensation of silicon compound(s) undergoing hydrolytic condensation and optionally other elements of boron, aluminium, phosphorus, tin, lead, transition metals, lanthanides and actinides and/or precondensates derived from these compounds by the action of water or moisture, optionally in the presence of a catalyst or solvent. 0-35 Mole-% is derived from Si compounds of formula (I). The antistatic contains 0-30 mole-% amine and/or quaternary ammonium compound(s), which contain organic group(s) with group(s) capable of polymerisation and/or polyaddition, and 0-30 mole-% salt(s) of optionally substituted (meth)acrylic acid, the total amount of (I), compounds and salts with respect to the condensate being 1-30 mole-%: ZaSiXbR(4-a-b) (I) X = hydrogen, halogen, hydroxyl, optionally substituted alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or an amino group NR'2; Z = R<2>2N-(R<3>-NR<2>-)k-R<3>-, 1/m Am<->R<2>2N<+>-R<3>-, (HO-R<3>)2N-R<3>, Cl-SO2-R<3>-, (R<2>O)2P(O)-R<3>, 1/m Am<-)<R<2>2N)2C=S<+>-R<3>-, 3/n Kn<+)<<->OOC)2N-R<3>-N(COO<->)-R<3>-, 1/m Am<->H2C=C(R<2>)-R<3>-N<+)<R<2>2)-R<3>- or 1/m Am<-> H2C=C(R<2>)-CO-O-R<3>-N<+)<R<2>2)-R<3>- or a quaternary ammonium salt derived from one of these; R = optionally substituted alk(en)yl, (alkyl)aryl or arylalkyl; R' = H, alkyl or aryl; R<2> = H, optionally substituted alk(en)yl, (alkyl)aryl or arylalkyl; R<3> = optionally substituted alk(en)ylene or arylene; Am<-> = an anion with charge m; Kn<+> = a cation with charge n; a, b = 1, 2 or 3; a+b = 2, 3 or 4; and k = 0, 1, 2 or 3.

Description

The invention relates to an antistatic agent and a method for producing this antistatic agent. The invention also relates to the use of the antistatic agent for the production of antistatic coatings.

Plastic materials are naturally good insulators with surface resistances >10<14> Q and, due to their high specific electrical resistance, have the property that they can accumulate electrical charges on their surface. This leads to static charges which are particularly strong in the event of frictional stress. This is generally undesirable as e.g. dust particles are thereby attracted and retained on the surface. The presence of these particles leads on the one hand to soiling and on the other hand to roughened surfaces due to the emery effect during cleaning. People have therefore for a long time tried to prevent the charging of the surface, either temporarily or permanently, by means of various precautions. If the surface resistance is reduced by means of electrically conductive substances to a range of IO<6> to IO<11> Q, the electric charge can flow away in a controlled manner (K.-H. Kochem, H.-U. ter Meer, H. Millauer , Kunststoffe j£2 (1992) 575) .

In order to prevent the unwanted charging of plastic materials or to cause a rapid discharge of the surface, various antistatic agents are used in practice (Ullmann's Enzyklopådie der techn. Chemie, 4th edition (1978), volume 15). Thereby, a distinction is made between internal and external antistatic agents.

Internal antistatic agents are a component of the plastic material composition. After some time, they diffuse to the surface of the plastic material and there form an antistatic effective film, whereby, however, the danger remains that the film and the effect are reduced. The rule concerns high-molecular, long-chain compounds with polar groups, such as e.g.

polyhydric alcohols, such as glycerol or polyethylene glycols

esters of long-chain fatty acids and polyalcohols

amino alcohols of the type HO-CH2-CH2-NR-CH2-CH2-OH The mechanism of action for these groups is based on the change in the dielectric constant and the electrical polarizability of the surface.

External antistatic agents are applied to the surface as a film from an aqueous or alcoholic solution using a coating method and are thus effective immediately. The disadvantage of this method is that the layer is very easy to remove so that no lasting effect can be achieved. This type involves ionic compounds, such as e.g. quaternary ammonium salts, sulphonates or phosphates. The ionic structure causes a reduction of the surface resistance by means of ionic conductivity. Hygroscopic agents, such as e.g. ammonium salts, causes surface adsorption of water from the atmosphere so that the water's conductivity is responsible for the antistatic effect.

From DE 3435841 A1 the use of ether sulphonates as antistatic agents is known. Thereby, water-soluble salts of sulfonic acids, which are formed by sulfonation of alkenylalkyl polyglycol ethers with the formula R-0 (-CnH2nO) ^- R1 with sulfur trioxide and subsequent hydrolysis, are used as antistatic agents for plastic materials, especially for polyamide fibers.

When using an antistatic agent of a cationic or amphoteric surface-active agent, it is true that excellent antistatic properties can be achieved immediately after the treatment, which, however, cannot be maintained for a long time. When, on the other hand, an antistatic agent of a urethane polymer or urethane prepolymer is used, the antistatic properties can indeed be maintained for a long time, but these are however poor in comparison with the properties of the antistatic agent of the cationic or amphoteric surfactant.

From DE 3719502 C2 an antistatic agent is known which contains as an essential component a cationic and/or amphoteric, water-soluble or water-dispersible and heat-reactive, blocked urethane prepolymer, which in its molecule exhibits at least one cationic group and/or at least one amphoteric group as well as isocyanate groups, which are blocked with a thermally dissociable blocking agent. This antistatic agent is used for the treatment of fibres.

From DE 3924200 A1, the use of sulfated hydroxyalkyl-alkylpolyalkylene glycol ethers of the general formula R-O-(A) X-CH2-CH(OSO3M)-R1 as antistatic agents for synthetic fiber-containing textile fiber materials is known.

Polythiophenes and their use for the antistatic coating of plastic material mold parts and film foils based on cellulose triacetate, polyethylene terephthalate or polycarbonate, which are used as substrates for photographic film substrates, are known from EP 0340512 and EP 0440957. Furthermore, from DE 4211459 Al the preparation of a known antistatic agent for photographic materials, where a polythiophene is used as an antistatic substance which is produced by oxidative polymerization of the thiophene with at least 1.0 mol of peroxy acid salt/mol of thiophene.

Already from the large number of compounds proposed for antistatic purposes, it can be recognized that a universal, i.e. for all plastic materials and areas of application equally well suited antistatic agent could not be found until now. Furthermore, most of the proposed compounds on many plastic materials exhibit shortcomings such as lack of compatibility, little tendency to enrichment on the surface, or they only work under certain conditions, such as somewhat elevated relative humidity. Other compounds can only be used to a limited extent due to their toxic properties or their colour.

The task was therefore to find an antistatic agent for plastic materials that covers a wide range of applications. The aim of the present invention is thereby to provide an antistatic agent which gives the most diverse materials antistatic properties, which can be maintained for a long period of time. The antistatic agent must be able to be applied to any surface on the most diverse plastic materials and must adhere firmly and permanently and be non-toxic. The production of the antistatic agent and the antistatic treatment of the plastic materials must be simple, cost-effective and universal.

This task is solved with the help of the antistatic agent according to the invention.

The present invention thus relates to an antistatic agent which is characterized by the following features: • it contains one or more organically modified silicic acid (hetero)polycondensates; • the silicic acid (hetero)polycondensates are obtained by hydrolytic (partial) condensation of one or more hydrolytically condensable compounds of silicon and possibly other elements from the group B, Al, P, Sn, Pb, the transition metals, the lanthanides and the actinides, and/or precondensates derived from the above compounds, by the action of water or humidity and optionally in the presence of a catalyst and/or a solvent; • 0 to 35 mol% of the hydrolytically (partially) condensed compounds based on monomeric compounds are derived from silicon compounds of the general formula I in which the residues and indices are the same or different and have the following meaning: X = hydrogen, halogen, hydroxy, optionally substituted alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR' 2 ;

Z = R<2>2 N-(R<3->NR<2->)k-R<3-,> 1/ m A<me> R<2>2 Næ-R3 -, (HO-R<3 >)2 N-R<3->,

C1-S02-R<3->, (R<2>0)2 P(0)-R<3->, <1>/m Ame (R<2>2N)2<C=>S<æ ->R<3->, <3>/n K<næ>(e00C)2 N-R<3->N(COO<e>)-R<3->,

<1>/m A<me> H2C=C (R2 ) -R3 -N® (R22) -R3 - or

Vm A<me> H2C=C (R2) -CO-O-R3-N® (R22) -R3- or quaternary ammonium salts derived therefrom;

R = optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl;

R' = hydrogen, alkyl or aryl;

R<2>= hydrogen, optionally substituted alkyl, alkenyl, aryl,

alkylaryl or arylalkyl;

R<3> = optionally substituted alkylene, alkenylene or arylene;

A<me> = anion with charge number m

K<n®>= cation with charge number n

a = 1, 2 or 3;

b = 1, 2 or 3;

a+b = 2, 3 or 4;

k = 0, 1, 2 or 3;

• it contains, on the basis of monomeric compounds and calculated on the silicic acid (hetero)polycondensate and compounds II and III, 0 to 30 mol% of one or more compounds II which constitute amines and/or quaternary ammonium compounds, and each of which carries one or several organic residues with one or more polymerizable and/or polyaddable

groups; • it contains, on the basis of monomeric compounds and calculated on the silicic acid (hetero)polycondensate and compounds II and III, 0 to 30 mol% of one or more compounds III which constitute salts of the optionally substituted acrylic acid and/or the optionally substituted methacrylic acid; • as the sum of compounds I, II and III, calculated on the silicic acid (hetero)polycondensate and compounds II and III, amounts on the basis of monomeric compounds to 1 to 30 mol%.

The present invention also relates to a method for producing an antistatic agent according to the invention, which is characterized in that one or more hydrolytically condensable compounds of silicon and possibly other elements of the group B, Al, P, Sn, Pb, the transition metals, the lanthanides and the actinides, and/or precondensates derived from the above-mentioned compounds under the influence of water or moisture and optionally in the presence of a catalyst and/or a solvent are subjected to a hydrolytic (part) condensation, further that 0 to 35 mol% of the hydrolytic (part )condensed compounds based on monomeric compounds, derived from silicon compounds of the general formula I

in which the residues and indices are the same or different and have the following meaning: X = hydrogen, halogen, hydroxy, optionally substituted alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR'2,

Z = <R2>2 N-(R<3->NR<2->)k-R3-, <1>/m Ame R22 N<®->R<3->, (HO-R<3> )2 N-R<3->,

C1-S02-R<3->, (R<20>)2 P(0)-R<3->, <x>/m Ame (R<2>2N)2 C=S<æ->R <3->, <3>/n K<næ> (<e>00C)2 N-R<3->N(COOe)-R<3->,

Vm A<me> H2C=C (R2) -R3-N®(R22) -R3- or

<1>/m A<me> H2C=C (R2) -CO-0-R3 -N® (R22) -R3- or quaternary ammonium salts derived therefrom;

R = optionally substituted alkyl, alkenyl, aryl,

alkylaryl or arylalkyl,

r' = hydrogen, alkyl or aryl,

R<2>= hydrogen, optionally substituted alkyl, alkenyl, aryl,

alkylaryl or arylalkyl,

R<3>= optionally substituted alkylene, alkenylene or arylene, A<me>= anion with charge number m

Kn® = cation with charge number n

a = 1, 2 or 3,

b = 1, 2 or 3,

a+b =2,3 or 4,

k = 0, 1, 2 or 3,

further that during or after the hydrolytic condensation, on the basis of monomeric compounds and calculated on the silicic acid (hetero)polycondensate and compounds II and III, 0 to 30 mol% of one or more compounds II which constitute amines and/or quaternary ammonium compounds are added, and which each carry one or more organic residues with one or more polymerisable and/or polyaddable groups, further that before, during or after the hydrolytic condensation, on the basis of monomeric compounds and calculated on the silicic acid (hetero)polycondensate and the compounds II and III adds 0 to 30 mol% of one or more compounds III

which constitute salts of the optionally substituted acrylic acid and/or the optionally substituted methacrylic acid, further that the sum of the compounds I, II and III on the basis of monomeric compounds and calculated on the silicic acid (hetero)polycondensate and the compounds II and III amounts to 1 to 30 mol% , and that volatile components are possibly removed and/or diluted with solvent if necessary.

The present invention further relates to the use of the antistatic agent according to the invention for the production of antistatic coatings.

The silanes of formula I and IV are hydrolyzable over the residues X and the silane of formula IV is polymerizable over the residues Y. An inorganic network with Si-O-Si units is built up over the hydrolysable groups, while the C=C double bonds contained in the residue Y respectively epoxide groups during the construction of an organic network can be subjected to a polymerization or polyaddition. The possibly present compounds with the general formulas II and III can likewise be incorporated into the organic network via their polymerisable and/or polyadditable groups.

The antistatic agent according to the invention is optionally diluted with a solvent, applied using normal coating methods to the surface to be treated antistatic and dried. Contains the antistatic agent according to the invention compounds with the general

formula II or III or were silanes used with it

in general formula IV, then the coating process continues with a cure by polymerization or polyaddition.

For the antistatic effect of the antistatic agents i

according to the invention are the compounds I, II and III

in charge. These are firmly incorporated via covalent bonds in the organic-inorganic network. In the case of silanes of formula I, the anchoring takes place in the inorganic network and if the residues R and/or Z contain polymerisable or polyadditable groups, they are additionally fixed in the

organic networks. In the case of compounds II and III, the covalent binding takes place in the organic network. The sum of the proportions of the compounds I, II and III in the dried or cured antistatic coating is, on the basis of monomeric compounds, between 1 and 30 mol%.

The antistatic agents according to the invention offer the great advantage that they can indeed be used as external antistatic agents, i.e. that surfaces can later be provided with a layer of antistatic agent, but that the antistatic agents according to the invention do not show those within the state of the art observed disadvantages with diffusion or solution from the surface. By binding the antistatic active substances into a silicic acid (hetero)polycondensate and by the excellent adhesion of the silicic acid (hetero)polycondensates to the various plastic materials, an excellent adhesion of the antistatic active substances to the various plastic material surfaces was thus achieved. The antistatic effect is clearly maintained longer. In addition, the antistatic agents according to the invention show the further great advantage that the plastic material surfaces can not only be treated antistatically with these agents, but the surfaces can also be treated to resist roughening.

The alkyl residues in the general formulas I, IV and V as well as in the compounds II and III are e.g. straight-chain, branched or cyclic residues with 1 to 20, especially 1 to 10 carbon atoms and are preferably lower alkyl residues with 1 to 6, preferably with 1 to 4 carbon atoms. Particular examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl.

The alkenyl radicals are e.g. straight-chain, branched or cyclic residues with 2 to 20, preferably 2 to 10 carbon atoms and preferably lower alkenyl residues with 2 to 6 carbon atoms, such as e.g. vinyl, allyl and 2-butenyl. Preferred aryl radicals are phenyl, biphenyl and naphthyl. Alkoxy, acyloxy, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, arylalkyl, alkylaryl, alkylene and alkylenearylene residues are preferably derived from the above-mentioned alkyl and aryl residues. Particular examples are methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, monomethylamino, monoethylamino, dimethylamino, diethylamino, N-ethylanilino, acetyloxy, propionyloxy, methylcarbonyl, ethyl -carbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenyl-ethyl and tolyl.

The preferred residues may optionally carry one or more substituents, such as e.g. halogen, alkyl, hydroxyalkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, monoalkylamino, dialkylamino, trialkylammonium, amido, hydroxy, formyl, carboxy, mercapto, cyano, isocyanato, nitro, epoxy, SO3H or PO4H2 .

Among the halogens, fluorine, chlorine and bromine and especially chlorine are preferred.

For a > 2 or b=2 respectively, the residues X and R can each have the same or a different meaning.

The residue Y is a straight-chain or branched organic residue with at least one C=C double bond and/or at least one epoxide group. The C=C double bonds can e.g. present in vinyl, allyl,

acrylic and/or methacrylic groups. The remainder Y displays 2 more

in 50, preferably 6 to 30 carbon atoms and without limitation of the general character are concrete examples:

Special examples of silanes of the general formula IV with epoxide groups in the residue Y are: Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltri(methoxyethoxy)silane , 3-glycidoxypropyltriacetoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, glycidoxymethyl(methyl)dimethoxysilane, glycidoxymethyl(ethyl)dimethoxysilane, glycidoxymethyl(phenyl)dimethoxysilane, glycidoxymethyl-(vinyl)dimethoxysilane, glycidoxymethyl(dimethyl)methoxysilane 2- glycidoxyethyl(methyl)dimethoxysilane, 2-glycidoxyethyl-(ethyl)dimethoxysilane, 2-glycidoxyethyl(dimethyl)methoxysilane, 3- glycidoxypropyl(methyl)dimethoxysilane, 3-glycidoxypropyl-(ethyl)dimethoxysilane, 3-glycidoxypropyl(dimethyl)methoxy- silane, 4-glycidoxybutyl(methyl)dimethoxysilane, 4-glycidoxybutyl(ethyl)dimethoxysilane, 4-glycidoxybutyl(dimethyl)methoxysilane, bis -(glycidoxymethyl)dimethoxysilane, bis-(glycidoxymethyl)diethoxysilane, bis-(glycidoxyethyl)-dimethoxysilane, bis-(glycidoxyethyl)diethoxysilane, bis-(glycidoxypropyl)dimethoxysilane, bis-(glycidoxypropyl)diethoxysilane, tris-(glycidoxymethyl)methoxysilane, tris-(glycidoxymethyl)ethoxysilane, tris-(glycidoxyethyl)methoxysilane, tris-(glycidoxyethyl)ethoxysilane, tris-(glycidoxypropyl)methoxysilane, tris-(glycidoxypropyl)ethoxysilane, 3,4-epoxycyclohexylmethyltrimethoxysilane, 3,4-epoxycyclohexyl -methyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylpropyltrimethoxysilane and 3,4-epoxycyclohexylbutyltrimethoxysilane.

In addition to the silanes with the general formulas I and/or IV, further hydrolytically condensable compounds of silicon or other elements of the group Al, Ti, Zr, B, P, Sn, Pb, the transition metals, lanthanides and actinides either as such or already in pre-condensed form.

It is preferred that at least 30 mol%, especially at least 70 mol% and especially at least 90 mol% on the basis of monomeric compounds of the starting materials used for the production of the silicic acid heteropolycondensates in the antistatic agents according to the invention are silicon compounds.

Among the hydrolyzable aluminum compounds possibly used for the production of the silicic acid heteropolycondensates in the antistatic agents according to the invention, the compounds having the general formula A1R°3 in which the radicals R° which are the same or different are selected from halogen, alkoxy, alkoxycarbonyl and hydroxy are particularly preferred . With regard to the more detailed (preferred) definition of these residues, reference can be made to detailed treatment in connection with the suitable hydrolyzable silicon compounds. The groups just mentioned can also be completely or partially replaced with chelating ligands (e.g. acetylacetone or acetoacetic acid ester, acetic acid).

Particularly preferred aluminum compounds are aluminum alkoxides and aluminum halides. In this connection, concrete examples can be mentioned as Al(OCH3)3, Al(OC2H5)3, Al(0-n-C3H7) 3, Al (0-i-C3H7)3, A1(0C4H9)3, Al (0 -i-C4H9) 3 , Al (0-s-C4Hg) 3 , AlCl3 and AlCl(OH)2. At room temperature liquid compounds, such as e.g. aluminum sec-butylate and aluminum isopropylate are particularly preferred.

Suitable hydrolyzable titanium and zirconium compounds, which can be used according to the invention, are compounds of the general formula M Xk Rx in which M means titanium or zirconium, the residues R and X are the same or different and are defined as in the case of the general formulas I and IV. This also applies to the preferred meanings, k means an integer from 1 to 4, especially 2 to 4, and 1 stands for 0, 1, 2 or 3, preferably for 0, 1 or 2. Particularly preferred are these compounds of such compounds where k is equal to 4. Particular preference is given to using zirconium compounds with the general formula V.

wherein R means optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl.

As in the case of the above-mentioned Al compounds, complexed Ti or Zr compounds can also be used. Further preferred complexing agents here are acrylic acid and methacrylic acid.

Concrete examples of applicable Zr and Ti compounds are TiCl4, Ti(O<C>2<H>5)4, Ti(OC3H7)4, Ti (0-i-C3H7)4, Ti(OC4H9)4, Ti (2-ethylhexoxy)4, ZrCl4, Zr(OC2H5)4, Zr(OC3H7)4, Zr(0-i-C3H7)4, Zr(OC4<H>9)4, Zr(2-ethylhexoxy)4 and ZrOCl2 .

Further hydrolysable compounds which can be used for the production of the silicic acid heteropolycondensates in the antistatic agents according to the invention are e.g. boron trihalides and boric acid esters, such as e.g. BC13, B(OCH3)3 and B(OC2H5)3, tin tetrahalides and tin tetraalkoxides, such as SnCl4 and Sn(OCH3)4 and vanadyl compounds, such as e.g. VOCI3 and VO(OCH3)3.

When using, in the context of the invention, various hydrolyzable compounds which can be hydrolysed by silicon compounds, it is possible to incorporate heteroatoms into the inorganic network and thus adapt the properties of the antistatic agents according to the invention to the requirements of the relevant application, e.g. with regard to roughness-resistant or optical properties.

The silanes with the general formulas I and/or IV are processed either alone or together with other hydrolytically condensable and possibly polymerizable components by hydrolytic condensation into silicic acid (hetero)polycondensates. Thereby, the inorganic network is built up by the hydrolytic condensation which can be further modified by the addition of further hydrolytically condensable compounds. In this silicic acid (hetero)polycondensate, further components, such as e.g. compounds of formula II or III, introduced by simple admixture. However, it is also possible to add these components already before or during the hydrolytic condensation.

For the construction of the inorganic network, i.e. for the production of the silicic acid (hetero)polycondensate, the silanes with the general formulas I and/or II, optionally with the addition of further hydrolyzable silanes as well as other co-condensable components and optionally in the presence of a catalyst and/or a solvent hydrolysed and poly-condensed by the action of water or moisture. This polycondensation takes place preferably according to the so-called Sol-Gel method, which is described e.g. in DE Offenlegungsschrift1 one 2758414, 2758415, 3011761, 3826715 and 3835968.

The production of the silicic acid (hetero)polycondensates in the antistatic agents according to the invention can take place in the usual manner within the range of poly(hetero)condensates. If practically exclusively silicon compounds are used, the hydrolytic condensation can in most cases take place by directly adding the necessary water to the silicon compounds to be hydrolysed and which are either present as such or dissolved in a suitable solvent at room temperature or with slight cooling (preferably with stirring) and in the presence of a hydrolysis and condensation catalyst) and then stirring the resulting mixture for some time (one to several hours).

In the presence of reactive compounds of Al, Ti or Zr, which

can also be present in a complex form, a gradual addition of the water is generally recommended. Regardless of the reactivity of the compounds present, the hydrolysis usually takes place at temperatures between -2 0 and 13 0°C, preferably between 0 and 3 0°C, respectively at the boiling point of the possibly used

solvent. As already indicated, the best way for the addition of water depends above all on the reactivity of the starting compounds used. Thus, one can e.g. add the dissolved starting compounds slowly to an excess of water or water is added in a portion or in portions to the possibly dissolved starting compounds. It can also be useful that the water is not added as such, but that it is introduced by means of aqueous organic or inorganic systems into the reaction system. In many cases, introducing the amount of water into the reaction mixture by means of moisture-containing adsorbents, e.g. of molecular sieves, and of aqueous, organic solvents, e.g. of 80% ethanol, proved particularly suitable. However, the addition of water can also take place by means of a chemical reaction where the water is released during the reaction. Examples of this are esterifications.

When a solvent is used, in addition to the lower aliphatic alcohols (e.g. ethanol or i-propanol) also ketones, preferably lower dialkyl ketones, such as acetone or methyl isobutyl ketone, ethers, preferably lower dialkyl ethers such as diethyl ether or dibutyl ether, tetrahydrofuran, amides, ester, especially acetic acid ethyl ether, dimethylformamide, amines, especially triethylamine, and their mixtures in question. The starting compounds do not necessarily all have to be present already at the beginning of the hydrolysis (polycondensation), but in certain cases it may even prove advantageous when only part of these compounds are first brought into contact with water and the remaining compounds are added later.

In order to avoid precipitation during the hydrolysis and polycondensation as much as possible, especially when using different compounds which can be hydrolysed by silicon compounds, the addition of water can be carried out in several stages, e.g. in three stages. Thereby, in the first step, e.g. one-tenth to one-twentieth of the amount of water required for the hydrolysis. After short stirring, the addition of a fifth to a tenth of the required amount of water can take place and after further short stirring the rest can finally be added.

The condensation time depends on the starting components in each case and their proportions, the possibly used catalyst, the reaction temperature, etc. In general, the polycondensation takes place at normal pressure, but can also be carried out at elevated or reduced pressure.

The polycondensate thus obtained is storage stable and can already be used as an antistatic agent as such or after partial or almost complete removal of the solvent used or of the solvent formed during the reaction. However, it is also possible before the intended use to add additional components (e.g. curing initiators, pigments, solvents, etc.). In some cases, it has proven advantageous to replace the excess water and the formed or possibly further added solvent in the product obtained after the polycondensation, in order to stabilize the polycondensate. For this purpose, the reaction mixture can be evaporated, e.g. in vacuum at a slightly elevated temperature (up to a maximum of 80°C) insofar as it can still be taken up in another solvent without problems.

In preferred embodiments of the antistatic agent according to the invention, the anions A<me> of the general formula I are halide ions. Particularly preferred are Cl<e >ions. In further preferred embodiments of the antistatic agents according to the invention, the cations K<n®> of the general formula I are alkali or alkaline earth ions.

In further preferred embodiments of the antistatic agents according to the invention, silanes of the general formula I are used, optionally in precondensed form, Cl6 H2C=CH-CH2-Ne(CH3)(CH2CH=CH2)-C3H6-Si(OCH3)3 ,

Cl6 H2C=C(CH3)-CO-0-C2H4-N®(CH3)2-C3H6-Si(OCH3)3l

Cle (CH3)3N<e-C>3H6-Si(OCH3)3, Cl<e> C14H29(CH3)2N<®->C2H4-Si(OCH3)3, H2N-<C>3H6-Si(OCH3)3, Cl<e> H3N-C3H6-Si(OCH3)3, (CH3)2N<®->C3H6-Si(OCH3)3, Cle (CH3)2NæH-C3H6-Si(OCH3)3, H2N-C2H4-NH- C2<H>4-NH-C2H4-Si(OCH3)3, Cl6 H3Ne-C2H4-NH-C2H4-NH-C2H4-Si(OCH3)3,

(HO-C2<H>4)2N-C2H4-Si(OC2H5)3 or Cl<e> (HO-C2<H>4)2N<®>H-C2<H>4-Si(OC2<H> 5)3 or a mixture of these.

If the antistatic agent according to the invention contains compounds II, these can be added either as amines or as quaternary ammonium compounds. If amines are used, their quaternization can be carried out by adding corresponding compounds before, during or after the hydrolytic condensation. Such quaternization agents are e.g. HCl or alkyl halides. If compounds II are used, it is preferred that these carry one or more acrylate, methacrylate, acrylic acid amide or methacrylic acid amide groups. Quite particularly preferably, the following compounds are used:

CH2=CH-CO-0-C2H4-N<®>(CH3)3 Cl<8>,

CH2=C(CH3)-CO-NH-C3H6-N(C<H>3)2, CH2=CH-CO-0-C2H4-N(CH3)2 or CH2=C(C<H>3)- CO-NH-C3H6-N<®>(CH3)3Cl<e>

The antistatic agent according to the invention can

i contain salts of substituted or unsubstituted acrylic or methacrylic acids. Particularly preferred are CH2=CH-CO-O<e>Li<®>, CH2<=>CH-CO-O<e>Na<®>, CH2<=C>H-CO-O<e>K< ®>, [CH2=CH-CO-O<e>]2Ba<2®> or [CH2<=C>H-CO-O<e>]2Pb<2®.>

The antistatic effect of the antistatic agent according to the invention can be further increased by adding heteropolar compounds. Preferably, LiCl, LiC104, HC1 or H3P04 or the following silanes are used for this: (CH3)3Si-CH2-CH2-S<0>3<e>Na<®>, (CH3)3Si-C=C-CH2-P <®>(C6H5)3Br°, (CH3)3Si-CH2-CH2-COOeNa® or (CH3)3Si-OeK®.

When adding amino alcohols, e.g. of

HO-CH2-CH2-NR-CH2-CH2-OH, the antistatic effect of the antistatic agent according to the invention can likewise be further increased.

With the help of design examples, the antistatic agent according to the invention and its production are illustrated in more detail. The following abbreviations are used:

GLYMO : Glycidoxypropyltrimethoxysilane

Mi : Methylimidazole (hydrolysis catalyst)

Silane GF 20: 3-triethoxysilylpropyl-succinic anhydride

MEMO : 3-methacryloxypropyltrimethoxysilane

MAS : Methacrylic acid

Example 1:

S<y>nthesis leave<p>:

1), 2) and 3) are weighed together and stirred for 1.5 hours at approx. 20°C. A clear mixture is created. 4) tip in and stir briefly. 5) is added slowly under ice cooling and stirred for 1 hour. 6) is added slowly under ice cooling. The result is a colorless clear mixture which after approx. Stirring for 30 minutes becomes somewhat viscous. After pressure filtration, the mixture is placed in an ultrasonic bath for 15 minutes until it is air-free and then used for coating.

Coating:

Substrate: 6 boards + 4 plates

Coating : deep centrifugation

Pretreatment: ethanol + ultrasound + corona discharge Curing: 2 hours 13 0°C

Antistatic test: plates: positive

board : positive

Binding: plates: 0 - 1

boards: 5

Optics : plates : light streaks

board : no streaks - fine particles Example 2:

S<y>nthesis leave<p>:

1), 2) and 3) are weighed together and stirred for 3 hours at approx. 18 - 20°C. A clear mixture is formed. 4) tip in and stir briefly. 5) is added slowly under ice cooling and stirred for 1 hour. 6) and 7) are added and stirred until everything is dissolved. A viscous mixture results. After pressure filtration, the mixture is placed in an ultrasonic bath for 15 minutes until it is air-free and then used for coating.

Bele<gg>in<g>:

Substrate: 6 boards + 4 plates

Coating : deep centrifugation

Pretreatment: ethanol + ultrasound + corona discharge Curing: 2 hours 13 0°C

Antistatic test: positive

Binding : plates : 0-1

boards: 5

Optics: slightly yellowish

plates : light lines

board : good

Example 3

S<y>nthesis leave<p>:

1), 2), 3) and 4) are weighed together and stirred for 3 hours at approx. 18-20°C. A faint yellow mixture results. 5) is tipped in and stirred for a short time. 6) is added slowly under ice cooling and stirred for 1 hour. A pale yellow clear mixture is formed. 7) is then added, the mixture is stirred for 15 minutes and filtered. The resulting mixture is used for the coating.

Coating A

Substrate: 6 boards + 4 plates

Coating: dipping

Pretreatment: ethanol + ultrasound + corona discharge

Curing: 2 hours / 13 0°C

Antistatic test: positive

Stapling : 0 - 1

Optics: good, no streaks, slightly yellowish

Beleg<g>in<g> B : A further 0.015625 mol = is added

1.8 g (85%) H3PO4 (total = 0.046875 mol)

(= 5.4 g H3P04)

Substrate: 6 boards + 4 plates

Coating: dipping

Pretreatment: ethanol + ultrasound + corona discharge Curing: 22 hours / 13 0°C

Antistatic test: positive

Binding : plates : O-l

board : 0-1.5

Optics: good, slightly yellowish

Example 4

S<y>nthesis leave<p>:

1), 2), 3) and 4) are weighed together and stirred for 3 hours at approx. 18-20°C. A faint yellow mixture is produced. 5) tip in and stir briefly. 6) is added slowly under ice cooling and stirred for 1 hour. A pale yellow, clear mixture is formed. 7) is then added, the mixture is stirred for 15 minutes and filtered. The resulting mixture is used for the coating

Coating A

Substrate: 6 boards + 4 plates

Coating: dipping

Pretreatment: ethanol + ultrasound + corona discharge

Curing: 2 hours / 13 0°C

Antistatic test: positive

Stapling : 0 - 1

Optics: good, no streaks

Coating B: A further 0.015625 mol = is added

1.8 g (85%) H 3 PO 4

Substrate: 6 boards + 4 plates

Coating: dipping

Pretreatment ethanol + ultrasound + corona discharge Curing: 2 hours / 13 0°C

Antistatic test: positive

Binding : plates : 0-1

boards: 5

Optics: good, no streaks, some particles Example 5

S<y>nthesis leave<p>:

The pre-hydrolyzate of 1) and 2) is stirred overnight until clear. 3) is added, 4) is slowly added dropwise under ice-cooling and the resulting mixture is stirred for 30 min. A yellow, clear mixture results. The pre-hydrolyzate of 1) and 2) is added thereto and stirred for 30 min. 5) is added slowly under ice cooling. Then stirring for 1 hour at room temperature. 6) is added and then stirred until everything is dissolved, the mixture is filtered under pressure and used for the coating.

Coating:

Substrate: 6 boards + 4 plates

Pretreatment: ethanol + ultrasound + corona discharge Curing: 2 hours / 13 0°C

Antistatic test: positive

Optics: good, slightly yellow colouring

Example 6

S<y>nthesis leave<p>:

The pre-hydrolyzate of 1) and 2) is stirred overnight until it is clear. 3) is added, 4) is slowly added dropwise under ice-cooling and the resulting mixture is stirred for 30 min. A yellow, clear mixture results. The pre-hydrolyzate of 1) and 2) is added thereto and stirred for 30 minutes. 5) is added slowly under ice cooling. Then stirring for 1 hour at room temperature. The mixture is then filtered under pressure and the resulting mixture is used for the coating.

Coating:

additive

medium: 1.5% IRG 184 g = 6.27 g

Substrate: 6 boards + 4 plates

Pretreatment: ethanol + ultrasound + corona discharge Curing: 2 UV lamps 1/2 performance 0.6 m/min.

Antistatic test: positive

Optics: good, slightly yellow colouring

The antistatic effect was assessed qualitatively according to the following method. After intensive rubbing with a cloth on the coated surface, the surface is held with approx. 1 cm distance over fine ash. With uncoated parts and with coatings without antistatic modification, ash particles were immediately drawn to the surface. This was not observed for all surfaces coated with the antistatic agents according to the invention.

Polycarbonate discs were coated with the antistatic agents obtained according to examples 1-6. The surface resistances were then measured. The following table shows the results.

Claims (25)

1. Antistatic agent, characterized by the following features: • it contains one or more organically modified silicic acid (hetero)polycondensates,• • the silicic acid (hetero)polycondensates are obtained by hydrolytic (partial) condensation of one or more hydrolytically condensable compounds of silicon and possibly other elements from group B , Al, P, Sn, Pb, the transition metals, the lanthanides and the actinides, and/or precondensates derived from the above-mentioned compounds, by the action of water or moisture and possibly in the presence of a catalyst and/or a solvent; 0 to 35 mol% of the hydrolytically (partially) condensed compounds on the basis of monomeric compounds are derived from silicon compounds of the general formula I in which the residues and indices are the same or different and have the following meaning: X = hydrogen, halogen, hydroxy, optionally substituted alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR' 2 ; Z = R<2>2 N-(R<3>-<N>R<2->)k-R<3>-, <1>/m A<me> R<2>2 N<®->R <3->, (HO-R<3>)2 N-R<3->, C1-S02-R<3->, (R<2>0)2 P(0)-R<3->, Vm A<me> (R<2>2N)2 C=S<æ->R <3>-,3/n Kn® (<e>00C)2 N-R<3->N(C00<e>)-R<3->,<1>/m A<me> H2C=C(R <2>)-R<3->N<®>(R<2>2)-R<3-> or<1>/m A<me> H2C=C(R2) -CO-0-R3- N® (R22) -R3- or thereof derived quaternary ammonium salts; R = optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl; R' = hydrogen, alkyl or aryl; R<2> = hydrogen, optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl; R<3> = optionally substituted alkylene, alkenylene or arylene; Ame = anion with charge number mK<n®> = cation with charge number n a = 1, 2 or 3; b = 1, 2 or 3; a+b =2, 3 or 4; k = 0, 1, 2 or 3; it contains on the basis of monomeric compounds and the rain on the silicic acid (hetero)polycondensate and the compounds II and III, 0 to 30 mol% of one or more compounds II which constitute amines and/or quaternary ammonium compounds, and each of which carries one or more organic residues with one or more polymerisable and/ or polyaddable groups; it contains on the basis of monomeric compounds and the rain on the silicic acid (hetero) polycondensate and the compounds II and III, 0 to 30 mol% of one or more compounds III which constitute salts of the optionally substituted acrylic acid and/or the optionally substituted methacrylic acid; being the sum of the compounds I, II and III, calculated on The silicic acid (hetero)polycondensate and compounds II and III, on the basis of monomeric compounds, constitute 1 to 30 mol%. 2. Antistatic agent as stated in claim 1, characterized in that it contains (partially) condensed silicon compounds which are derived from one or more compounds with the general formula IV wherein the residues and indices have the following meaning: R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl; X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR'2, where R' = hydrogen, alkyl or aryl; Y = straight chain or branched organic residue with 2 to 50 carbon atoms which may be interrupted by oxygen and/or sulfur atoms and/or by amino groups and which present at least one C=C double bond and/or at least one epoxide group, - a = 1, 2 or 3; b = 0.1 or 2; c = 1, 2 or 3, where a + b + c = 4. 3. Antistatic agent as stated in claim 1 or 2, characterized in that it contains (partially)-condensed zirconium compounds which are derived from one or more compounds of the general formula V wherein R stands for optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl. 4. Antistatic agent as specified in one or more of claims 1 - 3, characterized in that it contains one or more heteropolar compounds. 5. Antistatic agent as stated in claim 4, characterized in that it contains LiCl and/or LiCl04 and/or HC1 and/or H3P04. 6. Antistatic agent as stated in claim 4, characterized in that it contains (CH3)3Si-C<H>2-CH2-S03<e>Na<æ> and/or (CH3)3Si-C=C-CH2- P<®>(C6<H>5)3<B>r<e >and/or (CH3)3Si-CH2-CH2-COOeNae and/or (C<H>3)3Si-O<e>K® . 7. Antistatic agent as specified in one or more of claims 1 - 6, characterized in that it contains one or more amino alcohols. 8 . Antistatic agent as specified in one or more of claims 1 - 7, characterized in that it contains one or more compounds II which carry one or more acrylate, methacrylate, acrylic acid amide or methacrylic acid amide groups. 9. Antistatic agent as stated in claim 8, characterized in that it contains CH2<=>CH-CO-0-C2H4-N(C<H>3)2, CH2=CH-CO-0-C2H4-N<e >(CH3)3Cl<e>, CH2=C(CH3)-CO-NH-C3H6-N(CH3)2 or CH2=C(CH3)-CO-NH-C3<H>6-N<®>( CH3)3<C>l<e.> 10. Antistatic agent as specified in one or more of claims 1-9, characterized in that it contains one or more compounds III with the formula CH2=CH-CO-O<e>Li<®>, CH2=CH-CO-O<e>Na<®>, CH2<=C>H-CO -OeK<®>, [CH2<=>CH-CO-O<e>]2Ba<2®> or [CH2<=C>H-CO-O<e>]2Pb<2®>. 11. Antistatic agent as specified in one or more of claims 1 - 10, characterized in that in the general formula I the anions A<me> represent halide ions and/or the cations K<næ> represent alkali metal or alkaline earth metal ions. 12. Antistatic agent as specified in one or more of claims 1 - 11, characterized in that it contains (partially) condensed silanes derived from Cle H2C=CH-CH2-N®(CH3)(CH2CH=CH2)-C3H6-Si(OCH3)3, Cle H2C=C(CH3)-CO-0 -C2H4-Ne(CH3)2-C3H6-Si(OCH3)3, Cl<e> (CH3)3N<®->C3H6-Si(OC<H>3)3, Cl<e> C14H29(CH3)2N<®->C2<H>4-Si(OCH3)3, H2 <N-C>3H6-Si(OCH3)3, Cl<e> H3<N-C>3H6-Si(OCH3)3, (CH3)2N<®->C3H6-Si(OCH3)3, Cl<e> (CH3)2N<®>H-C3H6-Si(OCH3)3, H2N-C2H4-NH-C2<H>4-NH-C2<H>4-Si(OCH3)3, Cl<9> H3N<®-C>2H4-NH-C2H4-NH-C2H4-Si(OCH3)3, (HO-<C>2H4)2N-C2H4-Si(OC2H5)3 or Cl<e> (HO-C2<H>4)2<N®>H-C2H4-Si(OC2<H>5)3 or mixtures thereof. 13. Process for producing an antistatic agent as specified in one or more of claims 1-12, characterized in that one or more hydrolytically condensable compounds of silicon and possibly other elements of the group B, Al, P, Sn, Pb, the transition metals, the lanthanides and actinides, and/or precondensates derived from the above-mentioned compounds under the influence of water or moisture and possibly in the presence of a catalyst and/or a solvent are subjected to a hydrolytic (partial) condensation, further that 0 to 35 mol% of the hydrolytic ( part)condensed compounds on the basis of monomeric compounds, derived from silicon compounds of the general formula I in which the residues and indices are the same or different and have the following meaning: X = hydrogen, halogen, hydroxy, optionally substituted alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR'2, Z = <R2>2 N-(R<3->NR<2->)k-R<3->, Vm A<m>e R<2>2 N <®->R<3->, (HO-R<3>)2 N-R3 -, C1-S02-R<3->, (R<20>)2 P(0)-R<3->, <1>/m A<me> (R<2>2N)2 C=S<e ->R<3->,<3>/n K<n®>(e00C)2 N-R<3->N(COO<e>)-R<3->, Vm A<me> H2C=C (R2) -R3-N® (R22) -R3- or <1>/m A<me> H2C=C(R<2>)-CO-0-R<3- >N<®>(R<2>2)-R3- or quaternary ammonium salts derived therefrom; R = optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl, R' = hydrogen, alkyl or aryl, R<2> = hydrogen, optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl, R<3> = optionally substituted alkylene, alkenylene or arylene, A<me>= anion with charge number m Knæ = cation with charge number n a = 1, 2 or 3, b = 1, 2 or 3, a+b = 2, 3 or 4, k = 0, 1, 2 or 3, further that during or after the hydrolytic condensation, on the basis of monomeric compounds and calculated on the silicic acid (hetero)polycondensate and compounds II and III, 0 to 30 mol% of one or more compounds II which constitute amines and/or quaternary ammonium compounds are added, and which each carry one or more organic residues with one or more polymerisable and/or polyaddable groups, further that before, during or after the hydrolytic condensation, on the basis of monomeric compounds and calculated on the silicic acid (hetero)polycondensate and the compounds II and III adds 0 to 30 mol% of one or more compounds III which constitute salts of the optionally substituted acrylic acid and/or the optionally substituted methacrylic acid, further that the sum of the compounds I, II and III on the basis of monomeric compounds and calculated on silicic acid ( hetero) polycondensate and the compounds II and III make up 1 to 30 mol%, and that volatile components are possibly removed and/or any t dilute with solvent. 14. Method as stated in claim 13, characterized in that one or more silicon compounds with the general formula IV are used in which the radicals and indices have the following meanings: R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl, X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR'2, where R1 = hydrogen, alkyl or aryl, Y = straight chain or branched organic residue with 2 to 50 carbon atoms which may be interrupted by oxygen and/or sulfur atoms and/or amino groups and which present at least one C=C double bond and/or at least one epoxide group, a = 1, 2 or 3, b = 0, 1 or 2, c = 1, 2 or 3, where a + b + c = 4, and/or precondensates derived therefrom. 15. Method as stated in claim 13 or 14, characterized in that one or more zirconium compounds with the general formula V are used in which R stands for optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl, and/or precondensates derived therefrom. 16. Method as specified in one or more of claims 13 to 15, characterized in that one or more heteropolar compounds are added before, during or after the hydrolytic condensation. 17. Method as stated in claim 16, characterized in that LiCl and/or LiC104 and/or HC1 and/or H3P04 are added before, during or after the hydrolytic condensation. 18. Method as stated in claim 16, characterized in that (CH3)3Si-CH2-CH2-S03<e>Na<®> and/or (CH3)3<S>i-C is added before, during or after the hydrolytic condensation =C-CH2-P<®>(C6H5)3Br<e >and/or (CH3)3Si-CH2-CH2-COOeNa® and/or (CH3)3Si-O<e>K®. 19. Procedure as specified in one or more of claims 13 - 18, characterized in that one or more amino alcohols are added before, during or after the hydrolytic condensation. 20. Procedure as specified in one or more of claims 13 - 19, characterized in that before, during or after the hydrolytic condensation, one or more compounds II are added which carry one or more acrylate, methacrylate, acrylic acid amide or methacrylic acid amide groups. 21. Method as stated in claim 20, characterized in that before, during or after the hydrolytic condensation, CH2<=>CH-CO-0-C2H4-N(C<H>3)2, CH2=CH-CO- is added 0-C2H4-N<e>(CH3)3Cl<e>, CH2<=>C(CH3)-CO-NH-C3H6-N(CH3)2 or CH2<=>C(CH3)-CO-NH- C3H6-N<®>(CH3)3Cl<e> or a mixture of these. 22. Procedure as specified in one or more of claims 13 - 21, characterized in that before, during or after the hydrolytic condensation as a compound or compounds with formula III, CH2=CH-CO-O<e>Li<e>, CH2=CH-CO-OeNa® CH2=CH-CO-OeK is added ®, [CH2<=>CH-CO-O<e>]2Ba<2®> or [CH^CH-CO-O^Pb2® or a mixture of these. 23. Procedure as specified in one or more of claims 13 - 22, characterized in that compounds of the general formula I are added in which the anions A<me> stand for halide ions and/or the cations K<nffi> stand for alkali metal or alkaline earth metal ions. 24. Procedure as specified in one or more of the requirements 13 - 23, characterized in that Cle H2C=CH-CH2-N®(CH3)(CH2CH=CH2)-C3H6-Si(OCH3)3 is used as a compound of formula I, Cle H2C=C(CH3)-CO-0-C2H4- Ne(CH3)2-C3H6-Si(OCH3)3, Cl<6>(C<H>3)3N<e-C>3H6-Si(OCH3)3, Cl<e><C>14<H>29(C<H>3)2N<®->C2H4-Si (OCH3)3, H2N-C3H6-Si(OCH3)3l Cl<e> h^N-CgHg-SKOCH^, (C<H>3)2N<®->C3<H>6-Si(OCH3)3 , Cl<8> (CH3)2N<e>H-<C>3H6-Si(OCH3)3, H2N-<C>2H4-NH-C2<H>4-NH-C2<H>4-Si(OCH3 )3, Cle H3N®-C2H4-NH-C2H4-NH-C2H4-Si(OCH3)3, (HO-<C>2<H>4)2N-<C>2H4-Si(OC2<H>5)3 or Cl<e> (HO-C2<H>4)2<N®>H-C2H4 -Si(OC2<H>5)3 or a mixture of these, possibly in pre-condensed form. 25. Use of the antistatic agent as specified in one or more of claims 1-12 for the production of antistatic coatings.