WO2009077473A1

WO2009077473A1 - Flame-resistant plastisols containing expandable graphite

Info

Publication number: WO2009077473A1
Application number: PCT/EP2008/067485
Authority: WO
Inventors: Andreas Schmidt; Jutta Franklin; Rainer SCHÖNFELD; Andreas Ferencz
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2007-12-18
Filing date: 2008-12-15
Publication date: 2009-06-25
Also published as: DE102007061503A1

Abstract

The invention relates to flame-resistant plastisols containing expandable graphite as well as the use and production thereof.

Description

"Flameproof plastisols containing expandable graphite"

The present invention relates to flame-resistant plastisols containing expandable graphite and their use and preparation.

Plastisols are generally understood to mean dispersions of organic plastics in plasticizers which gel on heating to a higher temperature and cure on cooling to the plastic gel. The most widespread in practice today plastisols contain predominantly feinpulvriges polyvinyl chloride and / or copolymers of vinyl chloride. These finely powdered polymers are dispersed in a liquid plasticizer and form the pasty plastisol. Such plastisols are used for a variety of purposes. They are used, for example, as sealants, for impregnating and coating substrates made of textile materials, as cable insulation and as adhesive. In the automotive industry, plastisols are used for underbody protection, for seam sealing and sealing, for hood lining, as anti-dripping compound or as an adhesive. Depending on the intended use, these plastisols contain, in addition to the finely divided polymer powders and the liquid plasticizers, further additives.

PVC as a polymeric component in plastisols has the great advantage that these plastisols have good to very good flame retardancy properties due to the high halogen content, which is of great importance for many applications, such as in the automotive industry.

However, it is increasingly perceived as a disadvantage that PVC-based polymers split off hydrogen chloride when heated, which can lead to corrosion in manufacturing processes where heat is applied, or which often occurs at dangerously high levels in the event of fire or waste incineration. This instability of the PVC, which leads to brittleness and discoloration in addition to hydrochloric acid, requires the use z. T. toxic stabilizers, such. Lead and cadmium compounds.

As an alternative, therefore, plastisols of acrylic ester polymers ("acrylate plastisols") have been proposed. DE-PS 2 454 235 and 2 529 732 describe the use of acrylic polymers having a Tg> 35 ° C. with a coordination of Tg, particle diameter and composition of the dispersed polymer particle and specific plasticizer mixtures. US Pat. No. 4,071,653 and German Pat. Nos. 2,543,542, 2,722,752 and 2,949,954 describe specially constructed methacrylate particles which, because they are composed of a particularly softener-compatible core and a poor softener-compatible shell, show good storage stability of the liquid plastisol. US Pat. No. 4,176,028, GB Pat. No. 1,598,579, DE Pat. Nos. 2,812,014, 2,812,015 and 2,812,016 disclose the use of acrylic or methacrylic polymers.

However, problematic with plastisols based on acrylic ester polymers is still the fire behavior. Due to the lack of halogen content, said plastisols have a poor to very poor flame retardancy, whereby their use in technical areas that make high demands on fire protection, such as in automotive interiors, is extremely limited.

The aim of the present invention is therefore to provide a predominantly PVC-free, in particular a predominantly halogen-atom-free plastisol, which is characterized by its good flame retardancy.

Surprisingly, it has now been found that certain plastisols which, in addition to at least one phosphorus-free plasticizer, expandable graphite, at least one phosphorus atom-containing compound and at least one particular metal hydroxide, have excellent flame retardant properties.

The present invention therefore relates to a plastisol containing, a) 10 to 30 wt .-% of particles comprising a halogen atom-free polymer, b) 20 to 50 wt .-% of at least one phosphorus-free compound as a plasticizer, c) 2 to 20 wt. % of at least one phosphorus atom-containing compound, d) 10 to 40 wt .-% of at least one metal hydroxide of the general formula M (OH) _x , wherein the metal M is selected from the group consisting of lithium, sodium, potassium, (x = 1) magnesium , Calcium (x = 2), aluminum and gallium (x = 3), e) 1 to 10 wt .-% expandable graphite, each based on the total amount of the plastisol.

In a preferred embodiment of the invention, the total sum of all components of the plastisol according to the invention gives 100 wt .-%. Without being bound by any particular theory, it is to be assumed that, inter alia, the physical and / or chemical interaction of the phosphorus atom-containing compound, the metal hydroxide according to the invention and the expandable graphite during the firing process produces a highly advantageous intumescent layer which prevents the access of oxygen or heat to the flame site difficult. The synergistic interaction of the said three components gives the plastisol according to the invention special flame retardant properties, it being noted that the omission of only one of the components mentioned leads to a significant acceleration of the burning rate. This emphasizes the highly advantageous interaction of the phosphorus atom-containing compound, the metal hydroxide according to the invention and the expandable graphite.

In a particularly preferred embodiment of the invention, the plastisol according to the invention is PVC-free, in particular halogen atom-free. This has the advantage that when heating the plastisol according to the invention, such as in heat-based manufacturing processes or in the case of fire, no hydrogen chloride is split off, whereby the burden on humans and the environment is significantly reduced compared to conventional PVC plastisols.

In a further preferred embodiment of the invention, at least 80%, preferably at least 90% and very preferably at least 94% of the particles according to the invention comprising a halogen atom-free polymer have a maximum extent in each spatial direction of 250 nm to 500 μm. A maximum extent of the particles according to the invention in each spatial direction is particularly preferably from 500 nm to 250 μm, preferably from 750 nm to 100 μm and very preferably from 900 nm to 90 μm.

The particle size can be determined by means of suitable methods known to the person skilled in the art, such as laser diffraction or TEM (Transmission Electron Microscopy).

Said halogen-atom-free polymer according to the invention is preferably a methyl methacrylate homopolymer and / or copolymer of methyl methacrylate and at least one further copolymerizable monomer, wherein the copolymerisable monomer is preferably selected from the group of (meth) acrylic esters of aliphatic C ₂ to Cs alcohols, (meth) acrylic esters of aromatic alcohols , Polymerizable monomers comprising carboxylic acid or sulfonic acid groups, and / or any of their mixtures. The term (meth) acrylic acid ester is understood to mean both methacrylic esters and acrylic esters.

Suitable (meth) acrylic esters of aliphatic C ₂ to C ₈ alcohols and / or aromatic alcohols are preferably the (meth) acrylic acid esters of aliphatic alcohols, such as (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid i-butyl ester, (meth) acrylic acid t-butyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid octyl ester containing (meth) acrylic acid esters of cyclic aliphatic alcohols such as (meth ) cyclohexyl acrylate and the (meth) acrylic acid esters of aromatic alcohols, such as (meth) acrylic acid phenyl ester or (meth) acrylic acid benzyl ester.

Particularly preferred (meth) acrylic esters are (meth) acrylic acid ethyl esters, (meth) acrylic acid n-butyl esters, (meth) acrylic acid i-butyl esters and / or (meth) acrylic acid t-butyl esters and / or their any mixtures.

Suitable polymerizable monomers comprising carboxylic acid or sulfonic acid groups are preferably selected from the group consisting of (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid or allylsulfonic acid, their salts and / or any of their mixtures.

For the purposes of the invention, methylmethacrylic acid is a particularly preferred polymerizable monomer which comprises carboxylic acid groups.

Likewise preferred for the purposes of the invention is a copolymer of methyl methacrylate and various copolymerizable monomers, for example mixtures of (meth) acrylic acid and (meth) acrylic acid n-butyl ester.

Particularly preferred particles according to the invention comprising a halogen-atom-free polymer are alkyl methacrylate copolymers sold by Mitsubishi Rayon Co., Ltd., Tokyo, Japan under the trade name Dianal LP-3105 or 3106 or by Degussa Deutschland under the trade name Degalan®.

The proportion of the particles according to the invention comprising a halogen atom-free polymer, in the total amount of the plastisol is 10 to 30 wt .-%, preferably 15 to 28 wt .-% and most preferably 20 to 25 wt .-%. As at least one phosphorus atom-free compound as the plasticizer, any liquid or solid, indifferent organic substance can be considered which physically interacts with high polymer substances without chemical reaction and can form a homogeneous system with them; important is the very low volatility (low vapor pressure) of the plasticizer, since this otherwise could escape gradually during storage of the gelled plastisols, causing unwanted property changes occur.

Detailed definitions of the term plasticizer and the physical interaction between plasticizer and high polymer substances are given by K. Weinmann in "Coating with paints and plastics", Verlag W.A. Colomb, Stuttgart 1967, pages 47 to 158.

For the compatibility of a large number of commercially used plasticizers with different types of polymers see F. Stuehlen and L. Meier in the "Plastic Rundschau", 19, pp. 251 to 260 and 316 to 319 (1972).

The plasticizers used in the present invention are preferably those from the group of esters. The term esters also means liquid polyesters and natural oils, if they have an ester bond. When the natural oils have double bonds, it is also preferred that the double bond is at least partially in epoxidized form.

Preferably, the plasticizers from the group of esters are partial or full esters of mono- or polybasic carboxylic acids and monohydric or polyhydric alcohols. The alcohols mentioned may have a saturated or unsaturated structure.

If aliphatic carboxylic acids are used, these preferably contain 1 to 30, particularly preferably 4 to 25, carbon atoms. If monohydric or polyhydric aliphatic alcohols are used for ester formation, these alcohols preferably have 3 to 30, particularly preferably 6 to 30, carbon atoms. If cycloaliphatic alcohols are used, these preferably contain 4 to 12, particularly preferably 5 to 10, carbon atoms. If aromatic alcohols are used, their number of carbon atoms in the alcohol molecule is preferably from 6 to 12 carbon atoms. Particularly preferred plasticizers in the context of the invention are esters of phthalic acid, adipic acid, sebacic acid, azelaic acid, citric acid, cyclohexanecarboxylic acid and / or any desired mixtures thereof.

Very particular preference is given to dialkyl phthalates or cyclohexanedicarboxylic acid dialkyl esters, where the alkyl group comprises 6 to 30 C atoms, in particular 8 to 12 C atoms and very particularly preferably 8 to 10 C atoms. Highly preferred plasticizers according to the invention are, for example, C8 to C10 dialkyl phthalic acid esters, such as diisononyl phthalate (ex Benntag GmbH, Mülheim an der Ruhr, Germany).

The proportion of the at least one phosphorus-free compound as plasticizer in the total amount of the plastisol according to the invention is 20 to 50 wt .-%, preferably 30 to 40 wt .-% and most preferably 34 to 39 wt .-%.

The at least one phosphorus atom-containing compound, the at least one metal hydroxide and expandable graphite according to the invention exhibit a synergistic interaction in the concentration ranges mentioned, giving the plastisol special flame retardance properties. It should be noted that the omission of only one of the components mentioned leads to a significant acceleration of the burning rate in certain test bodies (see exemplary embodiments).

As phosphorus atom-containing compound in the context of the invention, all substances are to be considered in which the proportion of phosphorus based on the molecular weight of the phosphorus atom-containing compound at least 2 wt .-%, preferably at least 3 wt .-%, particularly preferably at least 4 wt .-% and most preferably at least 6 wt .-% is.

As phosphorus atom-containing compound inorganic or organic phosphates, phosphites or phosphonates and red phosphorus and / or any mixtures thereof can be used.

Preferably, the at least one phosphorus atom-containing compound is a plasticizer. This is particularly advantageous since, with constant material properties of the plastisol, the total proportion of the at least one phosphorus-free compound as plasticizer can be lowered and the total amount of phosphorus-containing compounds can be increased, which leads to an improvement in the fire protection properties of the plastisol. In a particularly preferred embodiment of the invention, the phosphorus atom-containing compound is a triorganophosphate. The term triorganophosphate is preferably understood to mean compounds of the general formula (I) and / or any mixtures thereof,

wherein R 1, R 2 and R 3 independently represent a substituted or unsubstituted, branched or linear alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl or aralkyl group.

If R1, R2 or R3 is an alkyl radical, this preferably contains 1 to 16, particularly preferably 1 to 10, carbon atoms. When R1, R2 or R3 is an aryl radical, it preferably contains from 6 to 10 carbon atoms. Alkyl-substituted aryl radicals are also preferred. The preparation of the compounds mentioned is known to the person skilled in the art and can be easily taken from the relevant literature.

Particularly preferred triorganophosphates are, for example, trialkyl phosphates, such as tri-2-ethylhexyl phosphate (Disflamoll® TOF ex Lanxess Germany), triaryl phosphates, such as tricresyl phosphate (Disflamoll® TKP ex Lanxess Germany), triphenyl phosphate (Disflamoll® TP ex Lanxess Deutschland), diphenyl cresyl phosphate (Disflamoll ® DPK ex Lanxess Germany) and alkylaryl phosphates, such as diphenyl-2-ethylhexyl phosphate (Disflamoll® DPO ex Lanxess Germany).

In another preferred embodiment of the invention, the phosphorus atom-containing compound is a polyphosphate, in particular an ammonium and / or sodium polyphosphate (eg sodium tripolyphosphate (Na ₅ P ₃ Oi ₀ )).

The proportion of the at least one phosphorus atom-containing compound in the total amount of the plastisol according to the invention is 2 to 20 wt .-%, preferably 8 to 16 wt .-% and most preferably 9 to 15 wt .-%.

As at least one metal hydroxide in the context of the invention, compounds of the general formula M (OH) _x are used, the metal M being selected from the group consisting of lithium, sodium, potassium (x = 1), magnesium, calcium (x = 2) , Aluminum, gallium (x = 3). Mixtures of said metal hydroxides are also O

prefers. Very particularly preferred metal hydroxides according to the invention are calcium hydroxide and / or aluminum hydroxide.

The proportion of the metal hydroxide according to the invention in the total amount of the plastisol according to the invention is 10 to 40 wt .-%, preferably 15 to 30 wt .-% and most preferably 20 to 25 wt .-%.

Without being bound by any particular theory, it is to be assumed that at higher temperatures, for example in the case of a fire, the metal hydroxides according to the invention convert to the corresponding oxides with elimination of water. The fire is cooled and the resulting water vapor forms a shielding gas layer. The residual metal oxide additionally lays insulating around the point of fire. However, the metal hydroxide alone is not enough to impart sufficient flame retardancy to the plastisol of the present invention. The desired properties are achieved only by the synergistic interaction of the phosphorus atom-containing compound, the metal hydroxide according to the invention and expandable graphite.

Expanded graphite is understood to mean special graphite compounds. Due to the layer structure of graphite, foreign atoms or molecules can be intercalated between the carbon layers in stoichiometric amounts. These graphite compounds, for example with sulfur or nitrogen compounds as a foreign molecule, which are also produced on an industrial scale, are referred to as expandable graphite. Under the action of heat, the layers are dispersed by thermolysis, whereby the properties of the expanded graphite are determined by the intercalation agent. The density of the expandable graphite is in the range of 1, 5 to 2.1 g / cm ³ , wherein preferably at least 80% of the expandable graphite particles have a maximum extension in each spatial direction of 10 to 1000 .mu.m, preferably from 20 to 500 microns. The particle size can be easily determined by means of suitable methods known to the person skilled in the art, such as laser diffraction or TEM (Transmission Electron Microscopy).

Particularly preferred expandable graphites are sold, for example, by Georg H. Luh GmbH, Germany under the trade names Expofoil GHL PX 955 and Expofoil GHL PX 901 1.

The proportion of expandable graphite in the total amount of the plastisol according to the invention is from 1 to 10 wt .-%, preferably 2 to 5 wt .-% and most preferably 2.5 to 4 wt .-%.

In a preferred embodiment of the invention, the plastisol contains at least one further additive selected from the group consisting of fillers, viscosity regulators, sedimentation inhibitors, flow improvers, fragrances, wetting agents, extenders, adhesion promoters, aging, oxidation or UV protection agents, matting agents, waxes and / or pigments.

Suitable fillers are organic and inorganic powders or fibrous materials, as well as mixtures thereof. As organic fillers, e.g. Starch, flax, hemp, cotton, cellulose and / or aramid fibers are used. As inorganic fillers, e.g. Carbonates, bicarbonates, silicates, zeolites, glass beads, glass fibers, metal oxides and / or carbon black are used. Preference is given to pulverulent inorganic substances, such as carbon black, talc, chalk, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz powder, alumina, carbon black being very particularly preferred as filler.

The proportion of the fillers in the total amount of the plastisol according to the invention is preferably 1 to 4 wt .-% and most preferably 2 to 3 wt .-%.

Suitable viscosity regulators, sedimentation inhibitors, flow improvers, fragrances, wetting agents, extenders, adhesion promoters, aging, oxidation or UV protection agents, matting agents, waxes and / or pigments are known to the person skilled in the art and their amounts can be easily determined by this, without much experimental effort become.

Another object of the present invention is a process for the preparation of the plastisol according to the invention, wherein a mixture of at least one phosphorus-free compound as plasticizer and at least one phosphorus atom-containing compound successive particles comprising a halogen atom-free polymer, at least one inventive metal hydroxide and expandable graphite and optionally further of the above given additives.

The mixture of said components is preferably stirred until a homogeneous distribution of all components is achieved. Subsequently, it is advantageous to remove the entrained air from the mixture by applying a vacuum. The plastisols produced according to the invention are processed by the usual plastisol technology (see, for example, HA Sarretnick, "Plastisols and Organosols", van Nostrand Reinhold Company, New York, 1972).

Likewise provided by the present invention is the use of the plastisol according to the invention for coating surfaces. Suitable surfaces are, for example, paper, cardboard, glass, leather, metal, textile, wood or plastic surfaces.

Typical examples of use in this connection are the use of the plastisol according to the invention for coating textile fabrics, such as tarpaulins or clothing fabrics, wherein the better light stability of the plastisol than the PVC is particularly advantageous. The use as anti-drumming compound and / or seam sealing and bonding in the automotive industry and the use as a coating and covering composition for adhesives is also possible.

Very particular preference is given to the use of the plastisol according to the invention for coating textiles, in particular for coating textiles which have been produced from natural and / or synthetic fibers.

In all applications, the particular flame retardancy of the present invention, preferably halogen-free plastisol of great advantage, since in this way the material safety of the respective products is significantly improved.

Further objects of the present invention are

the product of the thermal curing of the plastisol according to the invention,

a flame resistant fabric comprising a textile fiber and said thermal curing product, and

a method of making said flame-resistant fabric, comprising the steps of: a) applying a homogenous layer of the plastisol to a textile surface; b) thermal curing of the treated according to a) textile surface. The thermal curing is carried out preferably at temperatures of 50 to 350 ⁰ C, more preferably at 100 to 250 ⁰ C and most preferably at 110 to 150 ° C, wherein the curing time is to be chosen so that the plastisol invention cures completely, so that later no significant aftercuring occurs.

As textile fibers in the context of the invention, all known in the art natural and / or synthetic fibers are to be understood.

Natural fibers are understood to be fibers which have the same origin, for example, in the case of vegetable origin, obtained from cotton, or hemp or linen or another type of plant. In the case of animal origin of a natural fiber fibers belonging to a type of fiber are understood, for example, derived from sheep or llama or rabbit or any other species. It does not count the individual or company or local origin but only the biological genus of the organ of origin.

As a synthetic fiber type fibers are understood that share a certain basic chemical structure, such as polyester or polyurethane.

embodiments

1. plastisol production

In a flat ground cup, the liquid formulation ingredients are presented. While stirring, the halogen-free polymer is added in portions. Subsequently, the mixture is mixed with the metal hydroxide according to the invention. Once homogenization of the mixture is achieved, the expandable graphite and optional additives are added. The mixture is stirred for a further 5 minutes at medium stirrer power and for one minute at full power of the stirrer (RW 45, IKA, Staufen). The apparatus is then evacuated to remove entrained air from the mixture.

2. Preparation of the specimens

On one side of a polyester textile strip (basis weight 120 g / m ² , thread count 209/10 cm, thread count 310 dtex, 101 mm × 400 mm × approx. 10-20 μm), the respective plastisol is applied by means of a squeegee device, a homogeneous plastisol layer is formed on the textile surface whose layer thickness is 250 μm (± 10%). Subsequently, the thermal curing of the plastisol by using the specimens for 20 minutes at 140 ⁰ C in an oven (T 6030, Heraeus, Hanau) is provided.

3. Flame retardancy test

The testing of the burning behavior of the prepared specimens (see point 2) is carried out according to DIN 75 200 of September 1980.

The said standard is intended to determine the burning rate of automotive interior materials when exposed to a small pilot flame, the test being carried out on a horizontal sample assembly. The burning speed in mm / min is the quotient of that after the o.g. Norm measured focal length and the time required to cover this distance from the flame.

In a fire box (HMV, Atlas, Lentil Court), a horizontally mounted specimen clamped in a U-shaped support frame (355 x 102 x 20 mm) is exposed to a defined flame of moderate flame exposure for 15 seconds at one end of the specimen. It is determined whether and when the flame extinguishes or in which time the flame front passes through a burning distance lying between two measuring marks. In order to prove sufficient flame resistance for the respective field of application (eg automotive interior equipment), the arithmetic mean of the burning rate of five identical test specimens must be less than 110 mm / min.

The plastisols (PL) 1 to 6 shown in the table below were prepared (see point 1).

EPL = plastisol according to the invention; VPL = Comparative Plastisol Dianal LP-3105: Mitsubishi Rayon Co., Ltd., Tokyo, Japan

DINP: Brenntag GmbH, Mulheim an der Ruhr, Germany

Disflamoll DPO: Lanxess, Germany Expanded graphite Expofoil GHL PX 955, Georg H. Luh GmbH, Germany Calcium hydroxide: Mallinckrodt, Netherlands Carbon black: Trade commodity

The plastisols were used to coat textile strips made of polyester and then thermally cured (see point 2); the burning behavior of the specimens 1 to 6 thus produced was determined according to DIN 75 200. Specimen (EPK 1): Polyester + EPL 1; Layer thickness 250 μm specimen (EPK 2): polyester + EPL 2; Layer thickness 250 μm specimen (EPK 3): polyester + EPL 3; Layer thickness 250 μm Specimen (VPK 1): Polyester + VPL 1; Layer thickness 250 μm Specimen (VPK 2): Polyester + VPL 2; Layer thickness 250 μm Specimen (VPK 3): Polyester + VPL 3; Layer thickness 250 μm

The specific burning speeds can be found in the following table.

EPK = sample body according to the invention VPK = comparative sample body

The low burning speeds of EPK 1 to 3 show that only with plastisols which contain a phosphorus atom-containing compound, a metal hydroxide according to the invention and expandable graphite good to very good flame retardancy can be achieved.

In VPK 1 to 3 plastisol coatings are used, each containing only two of the three components mentioned. As a result, there is a significant increase in the burning rate. This shows the positive synergistic interaction of the phosphorus atom-containing compound, the metal hydroxide of the invention and the expandable graphite in the reduction of the burning rate.

Claims

claims

1) containing plastisol, a) 10 to 30 wt .-% of particles comprising a halogen atom-free polymer, b) 20 to 50 wt .-% of at least one phosphorus-free compound as a plasticizer, c) 2 to 20 wt .-% of at least one phosphorus atom-containing compound , d) 10 to 40 wt .-% of at least one metal hydroxide of the general formula M (OH) _x , wherein the metal M is selected from the group consisting of lithium, sodium, potassium (x = 1), magnesium, calcium (x = 2), aluminum and gallium (x = 3), e) 1 to 10 wt .-% expandable graphite, each based on the total amount of the plastisol.

2) plastisol according to claim 1, characterized in that the plastisol is halogen atom-free.

3) Plastisol according to at least one of claims 1 or 2, characterized in that the halogen-atom-free polymer according to claim 1 is a Methylmethacrylathomopolymer and / or represents a copolymer of methyl methacrylate and at least one other copolymerizable monomer.

4) plastisol according to claim 3, characterized in that in the case of a copolymer said copolymerizable monomer is selected from the group of (meth) acrylic acid esters of aliphatic C ₂ to C ₈ alcohols, (meth) acrylic acid esters of aromatic alcohols, polymerizable monomers, the carboxylic acid or sulfonic acid groups or any of their mixtures.

5) plastisol according to at least one of claims 3 or 4, characterized in that in the case of a copolymer, the particles have a core-shell structure, said core-shell structure, a core polymer and a shell polymer wherein the core polymer and the shell polymer are not identical and each comprises a copolymer according to claim 3. 6) plastisol according to at least one of claims 1 to 5, characterized in that the at least one phosphorus-free compound is selected as a plasticizer according to claim 1 from the group of esters.

7) Plastisol according to at least one of claims 1 to 6, characterized in that it is a plasticizer in the at least one phosphorus atom-containing compound.

8) plastisol according to at least one of claims 1 to 7, characterized in that it is at least one phosphorus atom-containing compound is a triorganophosphate, in particular a triaryl phosphate, trialkyl phosphate or alkylaryl phosphate.

9) plastisol according to at least one of claims 1 to 6, characterized in that it is at least one phosphorus atom-containing compound is a polyphosphate, in particular sodium and / or ammonium polyphosphate.

10) plastisol according to at least one of claims 1 to 9, characterized in that the at least one metal hydroxide according to claim 1 is calcium hydroxide and / or aluminum hydroxide.

1 1) A process for preparing a plastisol according to claim 1 to 10, characterized in that to a mixture of at least one phosphorus-free compound as a plasticizer and at least one phosphorus atom-containing compound successive particles comprising a halogen atom-free polymer, at least one metal hydroxide according to any one of claims 1 or 10, expandable graphite and optionally further additives are given.

12) Use of a plastisol according to any one of claims 1 to 10 for the coating of surfaces, in particular of textiles.

13) The product of the thermal curing of a plastisol according to any one of claims 1 to 10.

14) A flame-resistant textile product comprising a textile fiber and a product according to claim 13. 5) A process for the preparation of a flame-resistant fabric according to claim 14, comprising the following steps: a) application of a homogeneous layer of a plastisol according to one of claims 1 to 10 on a textile surface; b) thermal curing of the treated according to a) textile surface.