EP2643157A1 - Dint in expanded pvc pastes - Google Patents

Abstract

The invention relates to an expandable composition containing at least one polymer selected from among the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl methacrylate, and copolymers thereof, an expanding agent and/or foam stabilizer, and terephthalic acid diisononyl ester as a plasticizer, the average branching degree of the isononyl groups of the ester ranging from 1.15 to 2.5. The invention further relates to expanded molded articles and the use of the expandable composition for floor coverings, wallpapers, or synthetic leather.

Description

 DINT in foamed PVC pastes

The invention relates to a foamable composition comprising at least one polymer, in particular selected from the group consisting of polyvinyl chloride, Polyvinylidenchlohd, polyvinyl butyrate, polyalkyl methacrylate and copolymers thereof, a foaming agent and / or foam stabilizer and terephthaloyl disulfonate as plasticizer.

Polyvinyl chloride (PVC) is one of the most economically important polymers and is used both as rigid PVC as well as soft PVC in a variety of applications. Important applications include cable sheathing, floor coverings, wallpapers and frames for plastic windows. To increase elasticity, plasticizers are added to the PVC. These conventional plasticizers include, for example, phthalic acid esters such as di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP). Cyclohexanedicarboxylic acid esters, such as, for example, diisononylcyclohexanecarboxylic acid esters (DINCH), have recently become known as further plasticizers.

In many PVC articles, it is customary to reduce the weight of the products and thus also the costs due to the lower use of material by applying foam layers. For the user, a foamed product, for example in the case of floor coverings, can bring the advantage of better footfall sound insulation. The quality of the foaming is dependent on the formulation of many components, in addition to the type and amount of the foaming agent and the PVC type used and the plasticizer play an important role. Thus, it is known that good foaming can be achieved especially when well-gelling plasticizers (so-called rapid gels) are used at least proportionally in the formulation. It is known that with increasing chain length of the ester, the dissolving or gelling temperatures and thus the processing temperature of the soft PVC increase. As a consequence, the high temperatures cause discoloration of the PVC, which is undesirable in most applications. In order to reduce the processing temperatures, so-called fast gelators are added. These include, for example, benzoic beisononyl ester. The fast gels, however, have the disadvantage of leading to a large increase in viscosity (in the case of plastisols) over time due to their high solvation power (even when stored at room temperature), so that in turn viscosity-reducing agents must be added to compensate for this effect. These measures are costly and make the processing process expensive. It is further known that in many processing methods for polymer plastisols / polymer pastes, especially for PVC plastisols / PVC pastes, the processing speed depends in particular on the Plastisolviskosität, with a low plastisol viscosity allows higher processing speeds and thus increases the economics of the manufacturing process.

It is therefore a requirement in the production of PVC plastisols that during processing the lowest possible viscosity and a low gelling temperature is maintained. In addition, a high storage stability of the PVC plastisol is desired.

Plasticizers, which both significantly lower the gelation temperatures of a formulation and also keep the viscosity of the plastisol at a low level even after storage for several days, have hitherto hardly been known.

EP 1 505 104 describes a foamable composition which contains isononyl benzoate as plasticizer. The use of benzoic acid isonon esters as plasticizers has the considerable disadvantage that isononyl benzoates are very volatile, and therefore escape from the polymer during processing as well as with increasing storage and use time. This has in particular re in applications, for example, indoors significant disadvantages. Therefore, in the prior art, the isononyl benzoates are frequently used as plasticizer admixtures with customary other plasticizers, for example phthalic acid esters. The isononyl benzoate is also used as a fast gellant, the term fast gelling agent being used for plasticizers which allow for a comparatively faster (for example to diisononyl terephthalate) faster gelation and / or gelation at lower temperatures.

Other plasticizers known in the art include terephthalic acid alkyl esters for use in PVC. Thus, EP 1 808 457 A1 describes the use of dialkyl terephthalates, which are characterized in that the alkyl radicals have a longest carbon chain of at least four carbon atoms and have a total number of carbon atoms per alkyl radical of five. It is stated that terephthalic acid esters having four to five C atoms in the longest carbon chain of the alcohol are well suited as PVC fast-curing plasticizers. It is stated that this was particularly surprising because prior art such terephthalic acid esters were considered incompatible with PVC.

The document further states that the terephthalic acid dialkyl esters can also be used in chemically or mechanically foamed layers or in compact layers or primers.

WO 2009/095126 A1 describes mixtures of diisononyl esters of terephthalic acid and processes for their preparation. These diisononyl terephthalate mixtures are characterized by a certain average degree of branching of the isononyl radicals, which ranges from 1.0 to 2.2. The compounds are used as plasticizers for PVC.

Another disadvantage of the prior art plasticizers, when used in foamable compositions, is that often insufficient Foam heights can be achieved during foaming of the composition. In order to obtain sufficient foam heights, it is then necessary to use higher temperatures, but at the same time an increase in yellowness and thus an undesirable discoloration of the PVC foam is caused. Alternatively, the amount of propellant in the formulation or formulation can be increased, but this much more expensive.

The technical object of the invention is therefore to provide foamable compositions which have less volatile plasticizers and allow faster processing at lower temperatures.

This technical object is achieved by a foamable composition comprising a polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl methacrylate and copolymers thereof, a foaming agent and / or foam stabilizer and diisononyl terephthalate as plasticizer, wherein the average degree of branching of the isononyl groups of the ester in the range of 1, 15 to 2.5, preferably in the range of 1, 15 to 2.2, more preferably in the range of 1, 15 to 1, 95, particularly preferably in the range of 1, 25 to 1, 85 and all more preferably in the range of 1.25 to 1.45.

It has surprisingly been found that a foamable composition comprising a diisononyl terephthalate ester with the corresponding average degree of branching as a plasticizer enables faster processing in the preparation of foamed polymer compositions of polyvinyl chloride or polyvinylidene chloride. It has been found that, in comparison with plasticizers of the prior art with the claimed plasticizers, with increasing paste viscosity, as a result of increasing branching, a higher foam height is nevertheless achieved. This has the consequence that the corresponding pastes can be processed faster, as they already show higher foam heights in a shorter time and / or a total processing at lower temperatures is possible. This increases the efficiency of the process in terms of space / time yield and energy efficiency.

It has also been found that the paste viscosity of the foamable composition according to the invention, while in some cases significantly higher than paste viscosities with plasticizers of the prior art, but nevertheless a higher foaming can be achieved. This is surprising insofar as a higher paste viscosity usually also means a higher toughness / a higher "expansion resistance", and thus rather a lower expansion capability is expected.The higher foaming is possibly also due to the lower gelling speed of the foamable composition according to the invention Although this is a disadvantage in the prior art, it is a clear advantage here, which means that, despite a much lower gelling speed and increased paste viscosity, faster processing is possible in comparison with foamable compositions of the prior art.

A faster processing is important in that it can be done by a cheaper and more efficient production of the products. For example, in plastisol processing, e.g. As in the production of wall-mounted wallpaper, floor coverings and artificial leather, the corresponding machines when brushing the masses run much faster, and thus the productivity can be increased. In particular, the additional use of viscosity-reducing substances in the use of the diisononyl terephthalate according to the invention is not required, or only to a small extent.

Another advantage is that the foamable compositions can be processed at lower temperatures, and therefore also have a much lower yellowness value (caused by thermal degradation), at the same time a by the blowing agent (in particular azodicarbonamide) or its incomplete decomposition yellowness of the foamed composition is lower compared to prior art softeners.

Furthermore, it should be noted that the diisononyl terephthalates according to the invention are significantly less volatile than isononyl benzoates which are used in the prior art in foamable compositions. Thus, the use for indoor applications is facilitated since the plasticizers according to the invention are less volatile and escape less from the plastic. The determination of the average degree of branching of the isononyl groups of the diisononyl terephthalonyl ester is described below.

The average degree of branching of the isononyl radicals in the terephthalic acid diester mixture can be determined by ¹ H-NMR or ¹³ C-NMR methods. According to the present invention, the average degree of branching is preferably determined by means of ¹ H-NMR spectroscopy in a solution of the diisononyl esters in deuterochloroform (CDCl 3). To record the spectra, 20 mg of substance are dissolved in 0.6 ml of CDCl ₃ (containing 1% by mass of TMS) and filled into a 5 mm diameter NMR tube. Both the substance to be investigated and the CDCI3 used can first be dried over a molecular sieve in order to exclude any falsification of the measured values due to any water present.

The method of determining the average degree of branching is compared with other methods of characterization of alcohol residues, as described, for. As described in WO 03/029339 are advantageous since impurities with water have essentially no effect on the measurement results and their evaluation. The NMR spectroscopic investigations can in principle be carried out with any commercially available NMR instrument. For the present NMR spectroscopic investigations, an apparatus of the type Avance 500 from Bruker was used. The spectrum at a temperature of 300 K with a delay of d1 = 5 seconds, 32 scans, a pulse length of 9.7 seconds and a sweep width of 10000 Hz with a 5 mm BBO. Sampling head (broad band obser- ver, broadband observation). The resonance signals are recorded against the chemical shifts of tetramethylsilane (TMS = 0 ppm) as an internal standard. Other commercially available NMR devices give comparable results with the same operating parameters. The obtained ¹ H-NMR spectra of the mixtures of diisononyl esters of terephthalic acid have in the range of 0.5 ppm to the lowest of the lowest in the range of 0.9 to 1, 1 ppm of resonance signals, which are essentially by the signals the hydrogen atoms of the methyl group (s) of the isononyl groups are formed. The signals in the range of chemical shifts from 3.6 to 4.4 ppm can essentially be assigned to the hydrogen atoms of the methylene group which is adjacent to the oxygen of the alcohol or of the alcohol residue. The quantification is done by determining the area under the respective resonance signals, ie the area enclosed by the signal from the baseline.

Commercially available NMR devices have devices for integrating the signal surface. In the present NMR spectroscopic study, the integration was performed using the software "xwinnmr", version 3.5. Then, the integral value of the signals in the range of 0.5 to the minimum of the lowest trough in the range of 0.9 to 1, 1 ppm is divided by the integral value of the signals in the range of 3.6 to 4.4 ppm and so obtained an intensity ratio indicating the ratio of the number of hydrogen atoms present in a methyl group to the number of hydrogen atoms present in a methylene group adjacent to an oxygen. Since three hydrogen atoms are present per methyl group and two hydrogen atoms in each methylene group adjacent to an oxygen, the intensities must be divided by 3 and 2, respectively, in order to obtain the ratio of the number of methyl groups to the number of methyl groups adjacent to an oxygen in the isononyl group. As a linear primary nonanol, which only has a methyl group and an oxygen adjacent methylene group, contains no branching and therefore must have an average degree of branching of 0, must be subtracted from the ratio nor the amount of one. The average degree of branching V can thus according to the formula

V = 2/3 ^* l (CH ₃ ) / l (OCH ₂ ) -1 can be calculated from the measured intensity ratio. Herein, V = branching degree, l (CH ₃ ) = area integral, which is substantially assigned to the methyl hydrogen atoms, and l (OCH ₂ ) = area integral of the methylene hydrogen atoms adjacent to the oxygen.

The compositions according to the invention may comprise polymers selected from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylates, in particular polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA), fluoropolymers, in particular polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc, Polyvinyl alcohol (PVA), polyvinyl acetals, in particular polyvinyl butyral (PVB), polystyrene polymers, in particular polystyrene (PS), expandable polystyrene (EPS), acrylonitrile-styrene acrylate (ASA), styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS ), Styrene-maleic anhydride copolymer (SMA), styrene-methacrylic acid copolymer, polyolefins, in particular polyethylene (PE) or polypropylene (PP), thermoplastic polyolefins (TPO), polyethylene-vinyl acetate (EVA), polycarbonates, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TP U), polysulfide (PSu), biopolymers, in particular polylactic acid (PLA), polyhydroxyl butyric acid (PHB), polyhydroxylvaleric acid (PHV), polyesters, starch, cellulose and cellulose derivatives, in particular nitrocellulose (NC), ethylcellulose (EC), cellulose acetate (CA), cellulose acetate / butyrate (CAB), rubber or silicones and mixtures or copolymers of said polymers or their monomeric units. The compositions according to the invention preferably include PVC or homo- or copolymers based on ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, methacrylates, acrylates, acrylates or methacrylates with branched or unbranched alcohols attached to the oxygen atom of the ester group one to ten carbon atoms, styrene, acrylonitrile or cyclic olefins.

In a preferred embodiment, at least one polymer contained in the foamable composition is selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl methacrylate, and copolymers thereof.

In a particularly preferred embodiment, at least one polymer contained in the foamable composition is a polyvinyl chloride (homo- or copolymer).

In a further particularly preferred embodiment, the polymer may be a copolymer of vinyl chloride with one or more monomers selected from the group consisting of vinylidene chloride, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, methyl acrylate, ethyl acrylate or butyl acrylate.

Preferably, the amount of diisononyl terephthalate in the foamable composition is 5 to 120 parts by mass, preferably 10 to 100 parts by mass, more preferably 15 to 90 parts by mass, and most preferably 20 to 80 parts by mass per 100 parts by mass of polymer.

The foamable composition may optionally contain further additional plasticizers, except for diisononyl terephthalate, wherein the solvating and / or gelling ability of the additional plasticizers may be higher, equal or lower than that of the diisononyl terephthalate esters of the present invention. The mass ratio of the additional plasticizer used to the used The terephthalonyl diisononyl esters according to the invention are in particular between 1:10 and 10: 1, preferably between 1:10 and 8: 1, more preferably between 1:10 and 5: 1 and particularly preferably between 1:10 and 1: 1. In particular, the additional plasticizers are esters of orthophthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, trimellitic acid, citric acid, benzoic acid, isononanoic acid, 2-ethylhexanoic acid, octanoic acid, 3,5,5 Trimethylhexanoic acid and / or esters of butanol, pentanol, octanol, 2-ethylhexanol, isononanol, decanol, dodecanol, tri-decanol, glycerol and / or isosorbide and their derivatives and mixtures.

It is further preferred that the foamable composition according to the invention contains a foaming agent. This foaming agent can be a gas-bubble-forming compound, which is optionally used together with a so-called "kicker." Such kickers are catalysts which catalyze the thermal decomposition of the gas bubble-developing component and cause the foaming agent to react with evolution of gas and In principle, the foamable composition can be foamed chemically (ie by blowing agent) or mechanically (ie by incorporation of gases, preferably air) A compound which decomposes under the influence of heat into gaseous constituents, and thus causes a swelling of the composition The blowing agents for foaming suitable for the preparation of the polymer foams according to the invention include all types of known blowing agents, physical agents chemical and / or chemical blowing agents including inorganic blowing agents and organic blowing agents. Examples of chemical blowing agents are azodicarbonamide, azodiisobutyronitrile, benzenesulfonyl hydrazide, 4,4-oxybenzenesulfonyl semicarbazide,

Oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3-disulfonylhydrazide, p-

Toluenesulfonyl semicarbazide, N, N-dimethyl-N, N-dinitrosoterephthalamide and trihydrazine triazine, N = N-dinitrosopentamethylenetetramine, dinitrosotrimethyltriamine, sodium bicarbonate, sodium bicarbonate, mixtures of sodium bicarbonate and citric acid, ammonium carbonate, ammonium bicarbonate, potassium bicarbonate, diazoaminobenzene, diazoaminotoluene, Hydrazodicarbonamide, diazoisobutyronitrile, barium azodicarboxylate and 5-hydroxytetrazole.

At least one of the blowing agents used is particularly preferably azodicarbonamide, which liberates gaseous components such as N ₂ , CO ₂ and CO on reaction. The decomposition temperature of the propellant can be reduced by the kicker.

Mechanically foamed compositions are also referred to as "whipped foam".

In principle, the foamable compositions according to the invention may be, for example, plastisols.

It is further preferred that the foamable composition comprises a suspension, bulk, microsuspension or emulsion PVC. At least one of the PVC polymers contained in the composition according to the invention is particularly preferably a microsuspended PVC or an emulsion PVC. Most preferably, the foamable composition according to the invention comprises an emulsion PVC having a molecular weight expressed as K value (Fikent's constant) of 60 to 90 and particularly preferably 65 to 85. The foamable composition may furthermore preferably contain additives which are selected, in particular, from the group consisting of fillers / reinforcing agents, pigments, matting agents, heat stabilizers, antioxidants, UV stabilizers, costabilizers, solvents, viscosity regulators, foam stabilizers, flame retardants, adhesion promoters and processing agents. or processing aids (such as lubricants).

The thermal stabilizers neutralize u.a. hydrochloric acid split off during and / or after the processing of the PVC and prevent or retard thermal degradation of the polymer. Suitable thermal stabilizers are all customary polymer stabilizers, in particular all customary PVC stabilizers in solid and liquid form, for example based on Ca / Zn, Ba / Zn, Pb, Sn or organic compounds (OBS), as well as acid-binding phyllosilicates such as hydrotalcite. The mixtures according to the invention may have a content of from 0.5 to 10, preferably from 1 to 5, particularly preferably from 1.5 to 4, parts by mass per 100 parts by mass of polymer of heat stabilizer.

It is also possible to use so-called co-stabilizers with softening action, in particular epoxidized vegetable oils. Very particular preference is given to using epoxidized linseed oil or epoxidized soybean oil.

As a rule, the antioxidants are substances which specifically inhibit the radical polymer degradation caused, for example, by energetic radiation, for example by forming stable complexes with the resulting radicals. In particular, sterically hindered amines - so-called. HALS stabilizers -, sterically hindered phenols, phosphites, UV absorbers such. As hydroxybenzophenones, hydroxyphenylbenzotriazoles and / or aromatic amines included. Suitable antioxidants for use in the compositions of the invention are e.g. B. also in the "Handbook of Vinyl Formulating" (Editor: RFGrossman, J. Wiley &Sons; New Jersey (US) 2008). The content of antioxidants in the novel ßen foamable mixtures is in particular at most 10 parts by mass, preferably at most 8 parts by mass, more preferably at most 6 parts by mass and particularly preferably between 0.5 and 5 parts by mass per 100 parts by mass of polymer.

As pigments, both inorganic and organic pigments can be used in the context of the present invention. The content of pigments is in particular from 0.01 to 10 parts by mass, preferably from 0.05 to 8 parts by mass, more preferably from 0.1 to 5 parts by mass, per 100 parts by mass of polymer. Beispie- le of inorganic pigments are ΤΊΟ2, CdS, C0O / AI2O3, Cr ₂ 03. Known organic pigments are for example azo dyes, phthalocyanine pigments, dioxazine pigments, carbon black ( "Carbon black"), and aniline pigments. Also effect pigments z. B. based on mica Viscosity regulators may cause either a decrease in the viscosity of the paste or plastisol (viscosity-reducing reagents or additives) as well as the (curves) course of the viscosity as a function of the shear rate As viscosity-reducing reagents, it is possible to use aliphatic or aromatic hydrocarbons, but also carboxylic acid derivatives, such as the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate known as TXIB (Eastman), or else mixtures of carboxylic acid esters, wetting agents and dispersants, as described, for example, under the product / trade names, Byk, Viskobyk and Disperplast (Byk Chemistry) are used. Viscosity reducing reagents are added in proportions of 0.5 to 50, preferably 1 to 30, more preferably 2 to 10 parts by mass per 100 parts by mass of polymer.

As fillers mineral and / or synthetic and / or natural, organic and / or inorganic materials, such as. As calcium oxide, magnesium oxide, calcium carbonate, barium sulfate, silica, phyllosilicate, carbon black, bitumen, wood (eg., Powdered, as granules, micro-granules, fibers, etc.), paper, natural and / or Syn- thetikfasern be used. Particular preference is given to using calcium carbonates, silicates, talc, kaolin, mica, feldspar, wollastonite, sulfates, carbon black and microspheres (in particular glass microspheres) for the compositions according to the invention Common fillers and reinforcing agents for PVC formulations are also described, for example, in the "Handbook of Vinyl Formulating" (Ed .: RFGrossman, J.Wiley &Sons; New Jersey (US) 2008). Fillers are used in the compositions according to the invention in particular with a maximum of 150 parts by weight, preferably not more than 120, more preferably not more than 100 and especially preferably not more than 80 parts by weight per 100 parts by weight of polymer. In a particular embodiment, the proportion of the total fillers used in the formulation according to the invention is at most 90 parts by mass, preferably at most 80, more preferably at most 70 and especially preferably between 1 and 60 parts by mass per 100 parts by mass of polymer.

Commercially available foam stabilizers may be present in the composition according to the invention as foam stabilizers, as are mentioned, for example, in DE 10026234 C1. In particular, the preferred foam stabilizers contain surface-active substances such as, for example, alkali metal and / or alkaline earth metal salts of aromatic sulfonic acids such as, for example, the alkylbenzenesulfonic acids and also other aromatic compounds. Foam stabilizers may also be based on silicone compounds and / or contain surfactants. Soap / surfactant-based stabilizers contain, for example, calcium dodecylbenzenesulfonates as the active component. Silicone-based or soap-based foam stabilizers are available, for example, under the trade names Byk 8020 and Byk 8070 (Byk Chemie). The foam stabilizers are used in amounts of 1 to 10 parts by mass, preferably 1 to 8 and more preferably 2 to 4 parts by mass per 100 parts by mass of polymer. Another subject of the patent is the use of the foamable composition for floor coverings, wallpaper or artificial leather. Another object of the invention is a floor covering containing the foamable composition of the invention, a wall-mounted wallpaper containing the foamable composition of the invention or synthetic leather containing the foamable composition of the invention.

The diisononyl terephthalate esters having an average degree of branching of 1.15 to 2.5 are prepared as described in WO 2009/095126 A1. This is preferably carried out by transesterification of terephthalic acid esters with alkyl radicals having less than eight C atoms, with a mixture of isomeric primary nonanols. The preparation is particularly preferably carried out by transesterification of terephthalic acid dimethyl ester with a mixture of isomeric primary nonanols. Alternatively, the diisononyl terephthalate may also be prepared by esterification of terephthalic acid with a mixture of primary nonanols having the corresponding branching levels noted above.

For example, particularly suitable nonanol mixtures from Evonik Oxeno, which have an average degree of branching from 1.1 to 1.4, in particular 1.2 to 1.3, 35, and nonanol mixtures from Exxon Mobil (available on the market, for example) are suitable for the preparation of the diisononyl terephthalates. Exxal 9), which have a degree of branching of up to 2.4. Furthermore, the use of mixtures of low-branched nonanols, in particular of nonanol mixtures with a degree of branching of not more than 1, 5, and / or Nonanolgemsichen with marketable highly branched nonanols such as 3,5,5-trimethylhexanol is also possible in particular. The latter procedure allows the average degree of branching to be set within the given limits. The terephthalic acid mononyl esters used according to the invention are characterized as follows in terms of their thermal properties (determined by differential scanning calorimetry / DSC): 1. In the first heating curve (start temperature: -100 ° C, end temperature:

 +200 ° C; Heating rate: 10 K / min.) Of the DSC thermogram at least one glass transition point.

 2. At least one of the glass transition points detected in the abovementioned DSC measurement is below a temperature of -70.degree. C., preferably below -72.degree. C., more preferably below -75.degree. C. and particularly preferably below -77.degree C. In a particular embodiment, in particular if plastisols or polymer foams with particularly good low-temperature flexibility are to be produced, at least one of the glass transition points detected in the abovementioned DSC measurement is below a temperature of -75.degree. C., preferably below -77.degree preferably below -80 ° C, and more preferably below -82 ° C.

 3. In the first heating curve (start temperature: -100 ° C, end temperature:

 +200 ° C; Heating rate: 10 K / min.) Of the DSC thermogram no detectable melting signal (and thus a melting enthalpy of 0 J / g) on.

The glass transition temperature and the enthalpy of melting can be adjusted by the choice of the alcohol component used for the esterification or the alcohol mixture used for the esterification. The shear viscosity of the terephthalic acid esters used according to the invention at 20 ° C. is not more than 142 mPa ^* s, preferably not more than 140 mPa ^* s, more preferably not more than 138 mPa ^* s and particularly preferably not more than 136 mPa ^* s. In a particular embodiment, in particular when particularly low-viscosity plastisols are to be prepared which are suitable, for example, for very rapid processing, the shear viscosity of the terephthalic acid used according to the invention is at 20 ° C at a maximum of 120 mPa ^* s, preferably at most 1 10 mPa ^* s, more preferably at a maximum of 105 mPa ^* s and particularly preferably at a maximum of 100 mPa ^* s. The shear viscosity of the terephthalic acid esters according to the invention can be adjusted in a targeted manner by the use of isomeric nonyl alcohols of specific (average) branching for their preparation.

The mass loss of the terephthalic acid esters used according to the invention after 10 minutes at 200 ° C. is not more than 4% by mass, preferably not more than 3.5% by mass, more preferably not more than 3% by mass and particularly preferably not more than 2.9% by mass. In a particular embodiment, in particular when polymer foams with low emissions are to be produced, the mass loss of the terephthalic acid esters used according to the invention after 10 minutes at 200 ° C. is at most 3% by mass, preferably at most 2.8% by mass, particularly preferably at most 2 , 6 mass% and especially preferably at most 2.5 mass%. The mass loss can be specifically influenced and / or adjusted by the selection of the formulation constituents, in particular by the selection of diisononyl terephthalate esters with a certain degree of branching.

The (liquid) density of the terephthalic acid esters used according to the invention, determined by flexural vibrator, is at least 0.9685 g / cm ³ (with a purity of ot. GC analysis of at least 99.7 area% and a temperature of 20 ° C.). preferably at least 0.9690 g / cm ³ , more preferably at least 0.9695 g / cm ³ and especially preferably at least 0.9700 g / cm ³ . In a particular embodiment, the (liquid) density of the terephthalic acid esters used in accordance with the invention (at a purity of 1.0 g. GC analysis of at least 99.7 area% and a temperature of 20 ° C.) is at least 0.9700 g / cm ³ , preferably at least 0.9710 g / cm ³ , more preferably at least 0.9720 g / cm ³ and especially preferably at least 0.9730 g / cm ³ . The density of the terephthalic acid esters according to the invention can be adjusted in a targeted manner by the use of isomeric nonyl alcohols of specific (average) branching for their preparation. The preparation of the foamable composition according to the invention can be carried out in various ways. In general, however, the composition is prepared by intensive mixing of all components in a suitable mixing container. In this case, the components are preferably added successively (see also "Handbook of Vinyl Formulating" (Editor: RF Grorossman, J. Wiley & Sons, New Jersey (US) 2008).

The foamable composition of the invention can be used for the production of foamed moldings. The foamable compositions according to the invention particularly preferably comprise at least one polymer selected from the group consisting of polyvinyl chloride or polyvinylidene chloride or copolymers thereof.

Examples of such foamed products are imitation leather, floor or wall-mounted wallpaper, particularly preferred is the use of the foamed products in cushion vinyl floors ("CV floors") and wallpaper.

The foamed products of the foamable composition according to the invention are in particular prepared by first applying the foamable composition to a support or another polymer layer and foaming the composition before, during or after application, and / or or foamed composition is finally processed thermally (ie under the action of thermal energy, eg by heating / heating).

The foaming can be done mechanically, physically or chemically. Mechanical foaming of a composition or a plastisol is understood as meaning that air (or other gaseous substances) is introduced into the plastisol before application to the carrier, for example with sufficient vigorous stirring (so-called "impact foaming"), which causes foaming leads to the stabilization of the resulting Foam is usually a stabilizer necessary. The foam stabilizers used primarily determine cell structure, color and water absorption capacity of the finished foam. The choice of the type of stabilizer depends inter alia on the plasticizers to be used.

In addition to the foam stabilizer, other auxiliaries may also be added in order to influence and / or additionally stabilize the foam structure. These are, in particular, glycol dibenzoates. Glycol dibenzoates are understood essentially to mean diethylene glycol dibenzoate (DEGDB), triethylene glycol dibenzoate (TEGDB) and dipropylene glycol dibenzoate (DPGDB) or mixtures thereof.

Besides the mechanical foaming e.g. By vigorous stirring, the foamable compounds according to the invention can also be foamed physically with the aid of propellant gases, which, together with the plastisol according to the invention, are then mixed under pressure in a suitable technical apparatus and subsequently expanded under reduced pressure. As physical blowing agents, both inorganic and organic substances can be used. Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, oxygen and helium.

Organic propellants include aliphatic hydrocarbons having 1 to 6 carbon atoms, aliphatic alcohols having 1 to 3 carbon atoms, and fully or partially halogenated aliphatic hydrocarbons having 1 to 4 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, hexane, isohexane, heptane, octane, methylpentane, dimethylpentane, butene, pentene, 4-methylpentene, hexene, heptene, 2 , 2-dimethylbutane and petroleum ether. Aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. Fully and partially halogenated aliphatic hydrocarbons include chlorohydrocarbons, hydrofluorocarbons, and chlorofluorocarbons. Chlorohydrocarbons for use in this invention include methyl chloride, methylene chloride, ethyl chloride, ethylene dichloride, 1,1,1-trichloroethane, trichloromethane and carbon tetrachloride. Fluorocarbons for use in this invention include methyl fluoride, methylene fluoride, ethyl fluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a ), 1,1,2,2-tetrafluoroethane (HFC-1 34), pentafluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane and 1,1,1,3,3-pentafluoropropane. Partially hydrogenated chlorofluorohydrocarbons for use in this invention include chlorofluoromethane, chlorodifluoromethane (HCFC-22), 1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 1 , 1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1, 2-dichloro-1, 2,2-trifluoroethane (HCFC-123a) and 1-chloro-1, 2,2,2-tetrafluoroethane (HCFC-124). Fully halogenated hydrocarbons may also be used, but are not preferred for environmental reasons: fluorotrichloromethane (CFC-1 1), dichlorodifluoromethane (CFC-12), 1, 1, 2-trichloro-1, 2,2-trifluoroethane (CFC -1 1 3), 1, 2-dichloro-1, 1, 2,2-tetrafluoroethane (CFC-1 14), chloro-1, 1, 2,2,2-pentafluoroethane (CFC-1 15), trichlorofluoro- methane. In particular, foam stabilizers and / or further auxiliaries for influencing the foam structure are also used in physical foaming using propellant gases.

In the case of chemical foaming, the composition according to the invention contains a blowing agent which, under the influence of heat, decomposes completely or predominantly into gaseous constituents which cause the composition to expand. The decomposition temperature of the blowing agent can be significantly reduced by adding catalysts. These catalysts are known to the person skilled in the art as "kickers" and can either be added separately or preferably as a system together with the heat stabilizer. The composition according to the invention preferably contains at least one calcium, zinc or barium compound. The use of a foam stabilizer can optionally be dispensed with in the case of chemical foaming, in contrast to the mechanical foam. In contrast to the mechanical foam, in the case of chemical foams, the foam is not formed until the (thermal) processing, generally in a heated gelation channel, wherein initially the unfoamed composition is applied to the carrier, preferably by brushing. In this embodiment of the method, a profiling of the foam can be achieved by selective application of inhibitor solutions, for example via a rotary screen press. At the sites where the inhibitor solution was applied, expansion of the plastisol during processing is either not at all, or delayed. In practice, chemical foaming is used to a much greater extent than mechanical ones. Further information on chemical and mechanical foaming may be found, for example, in the "Handbook of Vinyl Formulating" (published by: RFGrossman, J.Wiley &Sons; New Jersey (US) 2008) or the technical textbook "Polymer Foams and Foam Technology" (D. V. Sendijarevic; Hanser Verlag; Munich; 2004). Optionally, a (further) profiling can also be achieved subsequently by means of the so-called mechanical embossing, for example by means of an embossing roller.

In both methods can be used as the carrier such materials that remain firmly connected to the foam produced, such as. B. woven or nonwoven webs. Likewise, however, the carriers can also be only temporary carriers, from which the foams produced can be removed again as foam layers. Such carriers may e.g. Metal tapes or release paper (duplex paper). Likewise, another, possibly even completely or partially (= pre-gelled), gelled polymer layer can function as a carrier. This is especially practiced on CV floors that are built up of multiple layers.

The final thermal processing takes place in both cases in a so-called gelation channel, usually a furnace, which is passed through by the applied on the support layer of the composition according to the invention, or in which the provided with the layer carrier is briefly introduced. The final one Thermal processing serves to solidify (gel) the foamed layer. In chemical foaming, the gelation channel can be combined with a device which serves to generate the foam. So it is z. For example, it is possible to use only one gelling channel in which the foam is chemically generated in the front part at a first temperature by decomposition of a gas-forming component and this foam in the rear part of the gelling channel at a second temperature which is preferably higher than the first temperature , semi-finished or final product is transferred. Depending on the composition, it is also possible that gelation and foaming occur simultaneously at a single temperature. Typical processing temperatures (gelling temperatures) are in the range of 130 to 280 ° C, preferably in the range of 150 to 250 ° C. The gelation is preferably carried out so that the foamed composition is treated at the stated gelling temperatures for a period of 0.2 to 5 minutes, preferably for a period of 0.5 to 3 minutes. The duration of the temperature treatment can be adjusted in continuously operating method by the length of the gelling channel and the speed at which passes through the foam having the carrier through this. Typical foaming temperatures (chemical foam) are in the range of 160 to 240 ° C, preferably 170 to 220 ° C and most preferably between 180 and 215 ° C.

In multilayer systems, the individual layers are usually first fixed in their form by a so-called pre-gelation of the applied plastisol at a temperature which is below the decomposition temperature of the propellant, after which further layers (for example a cover layer) can be applied. When all layers have been applied, gelation is carried out at a higher temperature - and, in the case of chemical foaming, also foaming. By this procedure, the desired profile can also be transferred to the cover layer. The foamable compositions of the present invention have the advantage over the prior art that they can be processed faster at lower temperatures, thereby significantly improving the efficiency of the PVC foam manufacturing process. Furthermore, the plasticizers used in the PVC foam are less volatile and thus the PVC foam is particularly suitable for interior applications in particular.

Even without further statements, it is assumed that a person skilled in the art can use the above description to the greatest extent. The preferred embodiments and examples are therefore to be considered as merely descriptive and not in any way limiting disclosure. Hereinafter, the present invention will be explained in more detail by way of examples. Alternative embodiments of the present invention are obtainable in an analogous manner.

Examples:

analytics:

1. Determination of purity

 The determination of the purity of the esters produced by GC is carried out with a GC machine "6890N" from Agilent Technologies using a DB-5 column (length: 20 m, inner diameter: 0.25 mm, film thickness 0.25 μΓη) from J & W Scientific and a flame ionization detector under the following conditions:

Start temperature oven: 150 ° C Final temperature oven: 350 ° C

(1) heating rate 150-300 ° C: 10 K / min (2) isothermal: 10 min. at 300 ° C

(3) Heating rate 300-350 ° C: 25 K / min.

Total running time: 27 min.

Inlet temperature injection block: 300 ° C split ratio: 200: 1

Split flow: 121, 1 ml / min total flow: 124.6 ml / min.

Carrier gas: Helium Injection volume: 3 microliters Detector temperature: 350 ° C Fuel gas: Hydrogen

 Flow rate of hydrogen: 40 ml / min. Flow rate air: 440 ml / min.

Makeup Gas: Helium Fluorite Makeup Gas: 45 ml / min.

The evaluation of the gas chromatograms obtained is carried out manually against existing reference substances (diisononyl orthophthalate / DINP, diisonononyl terephthalate / DINT); the purity is stated in area percent. Due to the high final contents of target substance of> 99.7%, the expected error due to lack of calibration to the respective sample substance is low. 2. Determination of the degree of branching

 The determination of the degree of branching of the esters produced by means of NMR spectroscopy is carried out by means of the method described in detail above. 3. Determination of the APHA color number

 The color number of the esters produced was determined in accordance with DIN EN ISO 6271 -2.

4. Determination of the density

The determination of the density of the esters produced takes place at 20 ° C. by means of bending oscillators in accordance with DIN 51757 method 4.

5. Determination of the acid number

 The acid number of the esters produced was determined in accordance with DIN EN ISO 21 14.

6. Determination of the water content

 The determination of the water content of the esters produced was carried out according to DIN 51777 part 1 (direct method).

7. Determination of intrinsic viscosity

 The determination of the intrinsic viscosity (shear viscosity) of the esters produced was carried out using a Physia MCR 101 (Anton Paar) with Z3 measuring system (DIN 25 mm) in the rotation mode using the following method:

The temperature of the ester and the measuring system were first brought to a temperature of 20 ° C. Subsequently, the following points were controlled by the software "Rheoplus": 1 . A preroll of 100 s ^"1 for the period of 60 s at which no readings were taken (to level any thixotropic effects that may occur and for better temperature distribution) 2. A frequency down ramp, starting at 500 s ^{" 1} and ending at 10 s ^"1 , divided into a logarithmic series with 20 steps, each with a measuring point duration of 5 s (verification of Newton's behavior).

All esters showed a Newtonian flow behavior. The viscosity values were given by way of example at a shear rate of 42 s ^'.

8. Determination of mass loss

 The determination of the mass loss of the ester produced at 200 ° C using a Mettler halogen dryer (HB43S). The following measurement parameters have been set:

 Temperature ramp: constant 200 ° C

Measurement record: 30 s

Measuring time: 10 min

Sample amount: 5 g

For the measurement, disposable trays made of aluminum (Mettler) and HS 1 fiber filter (glass fleece from Mettler) were used. After leveling and taring the balance, the samples (5 g) were evenly distributed on the fiber filter using a disposable pipette and the measurement started. For each sample, a duplicate determination was made, the measurements were averaged. The last measured value after 10 minutes is given as "loss of mass after 10 minutes at 200 ° C".

9. Carrying out the DSC analysis, determination of the enthalpy of fusion

The melting enthalpy and the glass transition temperature are determined by differential calorimetry (DSC) according to DIN 51007 (temperature range from -100 ° C. to + 200 ° C.) from the first heating curve at a heating rate of 10 K / min. Before the measurement The samples were cooled to - 100 ° C in the measuring instrument used and then heated at the specified heating rate. The measurement was carried out using nitrogen as a shielding gas. The inflection point of the heat flow curve is evaluated as the glass transition temperature. The determination of the enthalpy of melting takes place by integration of the peak area (s) by means of device software.

10. Determination of plastisol viscosity

 The viscosity of the PVC plastisols was measured using a Physica MCR 101 (Anton Paar) using the rotation mode and the measuring system "Z3" (DIN 25 mm).

The plastisol was first manually homogenized in the batch tank with a spatula, then filled into the measuring system and measured isothermally at 25 ° C. During the measurement, the following points were controlled:

1 . A pre-shear of 100 s ^"1 for the period of 60 s at which no measured values were recorded (to level any thixotropic effects that may occur).

2. A frequency ramp down, starting at 200 s ^"1 and ending at 0, 1 s ^{" 1} , divided into a logarithmic series with 30 steps each with a measuring point duration of 5 seconds.

The measurements were usually carried out (if not stated otherwise) after 24 hours storage / maturation of the plastisols. Before the measurements, the plastisols were stored at 25 ° C.

11. Determination of the gelling speed

The investigation of the gelling behavior of the plastisols was carried out in the Physica MCR 101 in oscillation mode with a plate-plate measuring system (PP25), which was operated under shear stress control. An additional tempering hood was connected to the unit for the best possible heat distribution.

Measurement parameters:

Mode: Temperature gradient (temperature ramp)

 Start temperature: 25 ° C

 End temperature: 180 ° C

 Heating / cooling rate: 5 K / min

 Oscillation frequency: 4 - 0, 1 Hz ramp (logarithmic)

 Angular frequency Omega: 10 1 / s

 Number of measuring points: 63

 Measuring point duration: 0.5 min

 Automatic gap tracking: Off

 constant measuring point duration

 Gap width 0.5 mm

Carrying out the measurement:

 On the lower measuring system plate, a drop of the plastisol formulation to be measured was applied with the spatula free of air bubbles. Care was taken to ensure that, after moving the measuring system, some plastisol could evenly escape from the measuring system (no more than approx. 6 mm around). Then the tempering hood was positioned over the sample and the measurement started.

The so-called complex viscosity of the plastisol was determined as a function of the temperature. Onset of gelling was evident in a sudden sharp increase in complex viscosity. The earlier this increase in viscosity began, the better the gelling ability of the system.

From the measured curves obtained, the temperatures at which a complex viscosity of 1000 Pa * s or 10,000 Pa ^* s was reached were determined by interpolation for each plastisol. In addition, the tangent method was used in the present Experimental setup determined maximum plastisol viscosity, and by precipitating a solder, the temperature at which the maximum plastisol viscosity occurs.

12. Preparation of the foam films and determination of the expansion rate

The foaming behavior was determined with the aid of a caliper knife suitable for soft PVC measurements (KXL047, Mitutoyo) with an accuracy of 0.01 mm. For the film production, a doctor blade gap of 1 mm was set on the doctor blade of a Mathis Labcoaters (type: LTE-TS, manufacturer: W. Mathis AG). This was checked with a feeler gauge and readjusted if necessary. The plastisols were knife-coated onto a release paper clamped in a frame (Warran Release Paper, Sappi Ltd.) using the doctor blade of Mathis Labcoater. In order to calculate the percentage of foaming, at 200 ° C / 30 seconds residence time first a gelled and unfoamed film was prepared. The film thickness (= initial thickness) of this film was at the indicated blade gap in all cases between 0.74 and 0.77 mm. The measurement of the thickness was carried out at three different locations of the film.

Subsequently, the foamed foils (foams) were also produced with the Mathis-Labcoater at 4 different oven residence times (60s, 90s, 120s and 150s). After the foams had cooled, the thicknesses were also measured at three different points. The mean of the thicknesses and the initial thickness were needed to calculate the expansion. (Example: (foam thickness starting thickness) / starting thickness ^* 100% = expansion).

13. Determination of the yellow value

The yellow value (index YD 1925) is a measure of yellow discoloration of a specimen. When evaluating foamed sheets, yellowness is generally of interest in two respects. On the one hand, it indicates the degree of decomposition of the propellant azodicarbonamide (= yellow in the undecomposed state) and, on the other hand, it is a measure of the thermal stability (discoloration as a result of thermal stress). The color measurement of the foam films was carried out with a Spectro Guide from the Byk-Gardner company. As background for the dyeing measurements, a (commercially available) white reference tile was used. The following parameters have been set:

Light type: C / 2 °

Number of measurements: 3

Display: CIE L ^* a ^* b ^*

Measurement index: YD1925

The measurements themselves were made at 3 different locations of the samples (for effect and smooth foams at a plastisol squeegee thickness of 200pm). The values from the 3 measurements were averaged.

Example 1 :

 Preparation of terephthalic acid esters

1.1 Preparation of Diisononyl Terephthalate (DINT) from Terephthalic Acid and Isononanol from Evonik Oxeno GmbH (Inventive)

644 g of terephthalic acid (Sigma Aldrich Co.), 1.59 g of tetrabutyl orthotitanate (Vertec TNBT, Johnson Matthey Catalysts) and a 4-liter stirred flask with water separator, attached intensive cooler, stirrer, dip tube, dropping funnel and thermometer 1440 g of a produced by the OCTOL process isononanol (Evonik OXENO GmbH) submitted, and esterified to 240 ° C. After 8.5 hours, the reaction was complete. Thereafter, the excess alcohol was distilled off to 190 ° C and <1 mbar. It was then cooled to 80 ° C and neutralized with 8 ml of a 10% by mass aqueous NaOH solution. Subsequently, a steam distillation was carried out at a temperature of 180 ° C and a pressure between 20 and 5 mbar. Thereafter, the batch was cooled to 130 ° C and dried at this temperature at 5 mbar. After cooling to <100 ° C, the mixture was filtered through filter aid (perlite). According to GC, an ester content (purity) of 99.9%. 1.2 Preparation of Diisononyl Terephthalate (DINT) from Dimethyl Terephthalate (DMT) and Isononanol from Evonik Oxeno GmbH (Inventive)

 776 g of dimethyl terephthalate / DMT (Oxxynova Co.), 1.16 g of tetrabutyl orthotitanate (Vertec TNBT, Johnson Matthey Co., Ltd.) were introduced into a 4 liter stirred flask having a distillation bridge with reflux divider, 20 cm Multifill column, stirrer, dip tube, dropping funnel and thermometer Catalysts) and initially 576 g of a total of 1440 g of isononanol (Evonik OXENO GmbH) submitted. It was slowly heated with stirring until no solid was visible. It was further heated until methanol accumulated on the reflux divider. The return divider was adjusted so that the head temperature remained constant at approx. 65 ° C. From a bottom temperature of about 240 ° C, the remaining alcohol was added slowly so that the temperature in the flask remained constant, and a sufficient reflux was maintained. From time to time, a sample was analyzed by GC and the content of diisononyl terephthalate and the content of methyl isononyl terephthalate determined. The transesterification was stopped at a content of <0.2 area% (GC) of methyl isononyl terephthalate. The work-up was carried out analogously to the work-up described in Example 1 .1.

1.3 Preparation of Diisononyl Terephthalate (DINT) from Terephthalic Acid and Isononanol from ExxonMobil (Inventive)

830 g of terephthalic acid (Sigma Aldrich Co.), 2.08 g of tetrabutyl orthotitanate (Vertec TNBT, Johnson Matthey Catalysts) and a 4-liter stirred flask with Wasserauskreiser, mounted intensive cooler, stirrer, dip tube, dropping funnel and thermometer 1728 g of an isononanol according to the polygas process (Exxal 9, ExxonMobil Chemicals) submitted, and esterified at 245 ° C. After 10.5 hours the reaction was complete. Thereafter, the excess alcohol was distilled off at 180 ° C and 3 mbar. It was then cooled to 80 ° C and neutralized with 12 ml of a 10 mass% aqueous NaOH solution. Subsequently, a steam distillation was carried out at a temperature of 180 ° C at a pressure between 20 and 5 mbar. Thereafter, the batch was dried at this temperature at 5 mbar and filtered after cooling to <100 ° C. According to GC, an ester content (purity) of 99.9%.

1.4 Preparation of diisononyl terephthalate (DINT) from terephthalic acid and n-nonanol (comparative example)

 In analogy to Example 1 .1, n-nonanol (Sigma Aldrich Co.) was esterified with terephthalic acid instead of isononanol, and worked up as described above. Upon cooling to room temperature, the product which, according to GC, has an ester content (purity) of> 99.8%.

1.5 Preparation of Diisononyl Terephthalate (DINT) from Terephthalic Acid and 3,5,5-Trimethylhexanol (Comparative Example)

 In analogy to Example 1 .1, 3,5,5-trimethylhexanol (OXEA GmbH) was esterified with terephthalic acid instead of the isononanol, and worked up as described above. Upon cooling to room temperature, the product which, according to GC, has an ester content (purity) of> 99.5%.

1.6 Preparation of Diisononyl Terephthalate (DINT) from Terephthalic Acid, Isononanol and 3,5,5-Trimethylhexanol (Comparative Example)

166 g of terephthalic acid (Sigma Aldrich Co.), 0.10 g of tetrabutyl orthotitanate (Vertec TNBT, Johnson Matthey Catalysts) and a 2-liter stirred flask with Wasserauskreiser, intensive cooler, stirrer, dip tube, dropping funnel and thermometer Alcohol mixture of 207 g of an isononanol according to the polygas process (Exxal 9, ExxonMobil Chemicals) and 277g 3,5,5-trimethylhexanol (OXEA GmbH) submitted, and esterified to 240 ° C. After 10.5 hours the reaction was complete. Thereafter, the stirred flask was connected to a Ciaisenbrücke with vacuum divider, and distilled off to 190 ° C and <1 mbar, the excess alcohol. It was then cooled to 80 ° C and neutralized with 1 ml of a 10 mass% aqueous NaOH solution. The mixture was then purified at a temperature of 190 ° C. and a pressure of <1 mbar by passing it through nitrogen (so-called "stripping") Approach cooled to 130 ° C, and dried at this temperature <1 mbar and filtered after cooling to 100 ° C. According to GC, an ester content (purity) of 99.98%. 1.7 Preparation of Diisononyl Terephthalate (DINT) from Terephthalic Acid, Isononanol and 3,5,5-Trimethylhexanol (Inventive)

166 g of terephthalic acid (Sigma Aldrich), 0.10 g of tetrabutyl orthotitanate (Vertec TN BT, Johnson Matthey Catalysts) and an Alko. Were in a 2-liter stirred flask with Wasserauskreiser, intensive cooler, stirrer, dip tube, dropping funnel and thermometer mixture of 83 g of an isononanol according to the polygas process (Exxal 9, ExxonMobil Chemicals) and 153 g of 3,5,5-trimethylhexanol (from OXEA GmbH) are initially charged and esterified to 240.degree. After 10.5 hours the reaction was complete. Thereafter, the stirred flask was connected to a Ciaisenbrücke with vacuum divider, and distilled off to 190 ° C and <1 mbar, the excess alcohol. It was then cooled to 80 ° C and neutralized with 1 ml of a 10 mass% aqueous NaOH solution. Thereafter, the mixture was purified by passage of nitrogen (so-called "stripping") at a temperature of 190 ° C. and a pressure of <1 mbar, after which the batch was cooled to 130 ° C. and at that temperature to <1 mbar dried and filtered after cooling to 100 ° C. According to GC, an ester content (purity) of 99.98%.

Characteristic material parameters for the esters obtained under 1 are summarized in Table 1. Table 1: Material parameters of the terephthalic acid esters prepared in Example 1 (inventive and comparative examples)

Product PureWhiteAPHA- Density AcidWhomeMass- DSC

(according to example) degree of color [g / cm ³ ] number of viscosity

(GC) (NMR) [-] [mg content [mPa ^* s] 10 minutes

[FI-%] [-] KOH / g] [%] @ 200 ° C Tg ΔΗ _Μ

 [% By mass] [° C] [Y / g]

Di (n-nonyl) terephthalate 99.75 0 n.bb. n.bb. 0.013 0.035 n.bb. 1, 2 no 158, (Example 1 .4 / comparison (solid) (solid)

example)

 Di (nonyl) terephthalate 99.97 1, 32 2 0.9743 0.01 0.007 96 2.2 - 86 0 (Example 1 .1 / according to the invention)

 Di (nonyl) terephthalate 99.8 2, 13 29 0.9724 0.001 0.003 136 2.2 - 78 0 (Example 1 .3 / according to the invention)

 Di (3,5,5-trimethylhexyl) - 99.76 2.99 n.b.b. n.bb. 0.016 0.01 n.bb. 2.7 no 107, terephthalate (example 1 .5 / (solid) (solid)

Comparative Example)

 Di (nonyl) terephthalate 99.98 2.49 14 0.9704 0.013 0.019 140 2.5-73 0 (Example 1 .7 / according to the invention)

 Di (nonyl) terephthalate 99.98 2.78 90 0.9681 0.03 0.01 1 145 2.6 -69 44.6 (Example 1 .6 / Comparative Example)

 Isononyl benzoate, VESTI 99.97 1, 3 7 0.9585 0.038 0.018 8.3 64.6-100 0 NOL® INB, from Evonik ***

Oxeno GmbH

(Comparative Example)

 Di (isononyl) phthalate, 99.95 1, 3 5 0.9741 0.016 0.023 76 3.7-86.0 VESTINOL® 9, from Evonik Oxeno GmbH (comparative example)

 n.bb. = Not determinable (for example: used cleaning method predicts liquid state of matter at room temperature). n.d. = not determined

Starting temperature (DSC):

The difference between the isononyl benzoate (INB) described in the prior art for the preparation of polymer foams and the terephthalic diisononyl esters used in accordance with the invention becomes clear above all from the drastic difference in volatility (loss in mass after 10 minutes at 200 ° C.). Here, a value which is 20 times higher is found for the isononyl benzoate. This high volatility means that INB can not be used in many indoor applications or only to a limited extent. When unbranched alcohol (n-nonanol, degree of branching = 0) is used to prepare the terephthalic acid esters, as expected, the unbranched terephthalate is obtained. This is a solid at room temperature which will not produce plastisol in a conventional manner. Even with a high degree of branching of about 3 as it is e.g. is obtained by the exclusive use of 3,5,5-trimethylhexanol as the alcohol component of the esterification with terephthalic acid, the terephthalate is present as a solid at room temperature, and can not be processed in the conventional sense. If a mixture of isononanol and 3,5,5-trimethylhexanol is used to prepare the terephthalic acid esters (see Examples 1 .6 and 1 .7), depending on the average degree of branching, products which are solid or liquid at room temperature are obtained. The solidification usually takes place with a time delay, ie does not start immediately after or during the cooling process, but only after several hours or several days.

Esters which show no melting signals when measured in the DSC and show a glass transition far below room temperature are best evaluated for their processability, since they are stored in unheated outer tanks worldwide at any time of the year, and without problems Pumps can be promoted. In the case of esters which show both a glass transition and one or more melt signals in the DSC thermogram, ie which show a partially crystalline behavior, no workability under European winter conditions (ie temperature up to -20 ° C), because the solidification sets in too early. Depending on the available results, whether melting points are present depends primarily on the degree of branching of the ester groups. If it is below 2.5 but above 1, esters are obtained which have no melting signals in the DSC thermogram and which are ideally suited for processing in expandable plastisols.

Example 2:

 Production of expandable / foamable PVC plastisols (without filler and / or pigment)

In the following, the advantages of the plastisols according to the invention with reference to an unfilled, non-pigmented, thermally expandable PVC plastisol are to be clarified. The following plastisols according to the invention are, inter alia, examples of thermally expandable plastisols which are used in the production of floor coverings. In particular, the following plastisols according to the invention are exemplary of foam layers which are used as backsheets in multilayer PVC floors. The formulations shown are kept general, and can or must be adapted by the skilled person to the specific application and use requirements existing in the respective field of application.

Table 2: Composition of the expandable PVC plastisols from Example 2. [All data in parts by mass]

^** = Comparative Example ^* = according to the invention

The substances and substances used are explained in more detail below:

Vinnolit MP 6852: microsuspension PVC (homopolymer) with K value (according to DIN EN ISO 1628-2) of 68; Fa. Vinnolit GmbH & Co KG.

VESTINOL® 9: diisononyl (ortho) phthalate (DINP), plasticizer; Fa. Evonik Oxeno GmbH.

 VESTINOL® INB: isononyl benzoate, plasticizer; Fa. Evonik Oxeno GmbH.

Unifoam AZ Ultra 7043: azodicarbonamide; thermally activated blowing agent; Fa. Hebron S.A.

Zinc oxide: ZnO; Thermal propellant decomposition catalyst; lowers the substantive decomposition temperature of the propellant; also acts as a stabilizer; "zinc oxide ^active® ", from Lanxess AG The zinc oxide was premixed with a sufficient (partial) amount of the plasticizer used in each case and then added. The liquid and solid formulation ingredients were weighed separately each in a suitable PE cup. By hand, the mixture was stirred with an ointment spatula so that no unwetted powder was present. The plastisols were mixed with a Kreiss dissolver VDKV30-3 (from Niemann). The mixing mixture was clamped in the clamping device of the dissolver stirrer. The sample was homogenized using a mixer disk (toothed disk, finely toothed, 0: 50 mm). The speed of the dissolver was continuously increased from 330 rpm to 2000 rpm and stirred until the temperature at the digital display of the thermo-controller reached 30.0 ° C. (temperature increase due to frictional energy / energy dissipation; NPCheremisinoff: "An Introduction to Polymer Rheology and Processing" (CRC Press, London; 1993), which ensured that the homogenization of the plastisol was achieved at a defined energy input, after which the plastisol was immediately heated to 25.0 ° C Example 3

 Determination of the Plastisol Viscosity of the Thermo-Expandable Piastisols Prepared in Example 2 After a Storage Period of 24 H (at 25 ° C.)

The measurement of the viscosities of the plastisols prepared in Example 2 was carried out as described under Analytik, item 10 (see above) using a Physica MCR 101 rheometer (Paar-Physica). The results are shown in the following table (3) as an example for the shear rates 100 / s, 10 / s, 1 / s and 0, 1 / s.

Shear viscosity of the plastisols from example 2 after 24 h storage at 25 ° C.

= Comparative Example ^* = according to the invention, the terephthalic acid ester used in the invention give PVC plastisols, which have a significantly lower paste viscosity in comparison to plastisols that are based on the current standard plasticizer DINP in the low shear rates while at a similar level as the comparable in the high shear rates DINP paste or slightly above it. Compared to the isononyl benzoate-based plastisol (6), the PVC plastisols of the present invention exhibit higher plastisol viscosity at high shear rates, while at lower shear rates, the same or even lower viscosity values are achieved. The dependence of the plastisol viscosity on the degree of branching of the terephthalic esters used is very good. While the terephthalic acid esters used according to the invention with a branching degree of the ester group up to 2.5 lead to plastisols with very good processing properties, the plastisol (5), which was produced on the basis of the higher branched comparative example 1 .6, shows a much higher shear viscosity, and leaves For example, they no longer readily process themselves by means of common application technologies (eg doctor blade application). The INB plastisol has an extremely low viscosity, which is also significantly below the viscosity of the DINP standard plastisol, especially at high shear rates. Expandable plastisols are thus made available by the terephthalic acid esters used according to the invention, which have similar processability to the high shear rates of the analogous DINP plastisols, but show a significantly more uniform course, for example during spray application, due to their lower plastisol viscosity at low shear rates.

Example 4:

Determination of the gelling behavior of the thermo-expandable plastisols prepared in Example 2

The investigation of the gelling behavior of the thermo-expandable plastisols prepared in Example 2 was carried out as under analytics, point 11. (see above), with a Physica MCR 101 in oscillation mode after storage of the plastisols at 25 ° C for 24 h. The results are shown in Table (4) below.

Table 4: From the gelation curves (viscosity curves) certain cornerstones of the gelling behavior of the thermo-expandable plastisols prepared according to Example 2.

= Comparative Example ^* = According to the invention

The thermally expandable plastisols according to the invention apparently have a disadvantage in terms of gelling properties in comparison with the DINP plastisol (= standard plasticizer). On the one hand they gel slower or at higher temperatures, on the other hand they only reach just under half of the final viscosity achieved with the comparable DINP plastisol (again at significantly higher temperatures). According to the common doctrine (eg F.Xing, CBPark in D. Klemmer, V.Sendijarevic (ed.), "Polymer Foams and Foam Technology", Hanser; Munich; 2004, chapter 9.3.2.9) you should therefore foam with The INB plastisol exhibits a very rapid gelation (or gelation at significantly lower temperatures) both in comparison with the DINP standard plastisol and in comparison with the terephthalate plastisols according to the invention while a maximum viscosity, which is well above the DINP standard. Example 5:

 Production of the foam films and determination of the expansion or foaming behavior of the thermo-expandable plastisols prepared in Example 2 at 200 ° C.

The foam foils were produced and the expansion / foaming behavior was determined in accordance with the procedure described under Analytik, Item 12. The average of the thicknesses and the initial thickness of 0.76 mm were used to calculate the expansion. The results are presented in the following table (5).

Table 5: Expansion of the polymer foams or foam foils produced from the thermally expandable plastisols (according to Ex. 2) at different furnace residence times in the Mathis Labcoater (at 200 ° C.).

= Comparative Example ^* = According to the invention

In comparison with the current standard plasticizer DINP, significantly higher foam heights / expansion rates are achieved after a residence time of 120 seconds. The corresponding INB plastisol (Plastisolrezeptur 6) achieved in all cases significantly lower expansion values, both in comparison with the DINP standard sample and in comparison with the plastisols invention. Thus, thermally expandable plastisols are provided which, despite obvious disadvantages in gelling behavior (see Example 4), have clear advantages in terms of thermal expansion. dierbarkeit, and thus allow faster processing or processing at lower processing temperatures.

 The completeness of the decomposition of the blowing agent used and thus the progress of the expansion process is also reflected in the color of the foam produced. The lower the yellowing of the foam, the further the expansion process has progressed. The yellowness value of the polymer foams or foamed sheets produced in Example 5, determined according to the analysis, item 13 (see above), is shown in the following table (6). TABLE 6 Yellow values (Y, D1925) of the polymer foams prepared according to Example 5.

= Comparative Example ^* = According to the invention

Although the expandable plastisols containing terephthalic acid esters according to the invention are still significantly higher in yellowness than the comparable DINP foam after a residence time of 90 seconds, after 120 seconds they reach, in some cases, a significantly lower level. The INB plastisol starts from a much higher level, is still higher than the DINP standard with a residence time of 90 s and ends at a comparable level as the plastisols, which were produced on the basis of the terephthalic acid esters used according to the invention. It is thus also apparent here that the terephthalic acid esters used according to the invention and the thermally expandable plastisols prepared with them according to the invention permit significantly faster processing in comparison with the existing standard softener DINP. Example 6:

 Production of Expandable / Foamable PVC Plastisols (Using Filler and Pigment) The advantages of the plastisols according to the invention based on a filler and pigment-containing thermally expandable PVC plastisol are to be clarified below. The following plastisols according to the invention are u.a. Exemplary for thermally expandable plastisols, which are used in the manufacture of floor coverings. In particular, the following plastisols according to the invention are exemplary of foam layers which are used as printable and / or inhibitable top side foams in multilayer PVC floors.

The preparation of the plastisols was carried out analogously to Example 2 but with a modified recipe. The weights of the components used for the different plastisols are shown in the following table (7).

Table 7: Composition of the filled and pigmented expandable PVC plastisols according to Example 6. [All data in parts by mass]

^** = Comparative Example ^* = according to the invention

The substances and substances used, which do not already result from the preceding examples, are explained in more detail below:

Calibrite OG: calcium carbonate; Filler; Fa. OMYA AG.

KRONOS 2220: Rutile pigment (Ti0 ₂ ) stabilized with Al and Si; White pigment; Company Kroenos Worldwide Inc.

Isopropanol: Cosolvent for lowering the plastisol viscosity and additive for improving the foam structure (Brenntag AG). Example 7:

 Determination of the Plastisol Viscosity of the Filled and Pigmented Thermo-Expandable Plastisols from Example 6 After a Storage Time of 24 H (at 25 ° C)

The measurement of the viscosities of the plastisols prepared in Example 6 was carried out as described under analytics, item 10 (see above), using a Rheometer Physica MCR 101 (from Paar-Physica). The results are shown in the following table (8) as an example for the shear rates 100 / s, 10 / s, 1 / s and 0, 1 / s.

Table 8: Shear viscosity of the plastisols from Example 6 after 24 h storage at 25 ° C.

= Comparative Example ^* = According to the invention The isononylbenzoate (INB) -based plastisol (comparative example, plastisol formulation 6) has the lowest shear viscosity at all shear rates shown. The plastisols according to the invention have, in comparison with the DINP used as a standard plasticizer, in some cases a considerably lower shear viscosity, which leads to significantly improved processing properties, in particular to a considerably increased application speed during coating and / or doctor application. The influence of the branching on the plastisol viscosity is clearly recognizable. The specimen measured as sample 5 (comparative sample) with a degree of branching of 2.8 shows already at low shear rates an order of magnitude higher viscosity compared to the other specimens, at higher shear rates the measurement had to be stopped because the measurement tolerance was exceeded. It is thus proved that such plastisols are not processable. On the other hand, according to the invention, plastisols are made available which, depending on the degree of branching chosen, have similar or significantly improved processing properties compared to plastisols which are based on the standard plasticizer DINP.

Example 8:

 Determination of the Gelation Behavior of the Filled and Pigmented Thermally Expandable Piastisols from Example 6 The investigation of the gelling behavior of the filled and pigmented thermally expandable plastisols prepared in Example 6 was carried out as described under Analysis, Item 11 (see above) using a Physica MCR 101 in oscillation mode a storage of Piastisole at 25 ° C for 24h. The results are shown in Table (9) below.

Table 9: From the gelation curves (viscosity curves) certain cornerstones of the gelling behavior of the filled and pigmented expandable plastisols prepared according to Example 6. Plastisol recipe 2 * 3 * 4 * 5 ** 6 **

(according to example 6)

 Achieving a plasticity of 82 1 13 1 17 1 18 1 18 67 sol viscosity of

1 .000 Pa ^* s at [° C]

 Reaching a plastic sol viscosity of

10,000 Pa ^* s at [° C]

Maximum Plastics 31,300 16,400 14,900 13,900 13,700 45,200 sol viscosity [Pa ^* s]

 Temperature at Er132 144 147 146 147 1 1 1 the max.

Plastisol viscosity [° C]

= Comparative Example ^* = According to the invention

As in the case of the unfilled thermally expandable plastisols (see Example 4, Table 4), the plastisol based on isononyl benzoate (INB) has the fastest gelation or the lowest gelling temperature of all the plastisols shown. As can also be seen in the case of the unfilled plastisols, there is also a considerable difference in the gelation behavior between the DINP plastisol (= standard) and the plastisols, which contain terephthalic acid mononate, with the plastisols with filler. Gelation is slower with terephthalic acid esters and only starts at much higher temperatures. Also, the maximum plastisol viscosity achievable by gelation is only about half that of DINP plastisol. It was therefore also to be assumed here that the foaming behavior of the plastisols, which contain terephthalic acid mononyl ester, is significantly worse than that of the DINP plastisol. Example 9:

 Preparation of the foam films and determination of the expansion or foaming behavior of the thermo-expandable plastisols prepared in Example 6 at 200 ° C.

The preparation of the foam films and the determination of the expansion behavior was carried out analogously to the procedure described under Analysis, item 12, however, using the filled and pigmented plastisols prepared in Example 6. The results are shown in Table (10) below.

Table 10: Expansion of the polymer foams or foam foils produced from the filled and pigmented thermally expandable plastisols (according to Ex. 6) at different furnace residence times in the Mathis Labcoater (at 200 ° C.).

* ^* = Comparative Example ^* = according to the invention

As expected, the expansion of plastisols containing fillers is significantly lower than those without fillers (see Example 5). As with the plastisols without filler, however, with the plastisols which contain the terephthalic acid esters used according to the invention, significantly higher foam heights are again achieved after a residence time of 120 seconds in comparison with the current standard plasticizer. The isononylbenzoate (INB) -based plastisol formulation (6), on the other hand, exhibits expansion only up to a residence time of 90 seconds, which is at the level of the DINP standard (1), but below that required by the According to the invention achieves the achievable paste (3), and then shrinks again. The INB final sample (after 120 seconds) has a significantly lower and completely unsatisfactory expansion in comparison with both the DINP standard and the plastisols which are based on the terephthalic acid esters used according to the invention. Although the comparative sample (5) based on highly branched diisononyl terephthalate has very good foamability, it is not suitable for industrial use because of its extremely disadvantageous theological behavior (see Tab. 8). Thus, thermally expandable plastisols with fillers are made available which, despite obvious disadvantages in the gelling behavior (see Example 8), have clear advantages in terms of thermal expandability.

 Even with plastisols with fillers (despite the content of white pigment) can be read off the completeness of the decomposition of the propellant azodicarbonamide used and thus the progress of the expansion process on the color of the foam produced. The lower the yellowing of the foam, the further the expansion process is completed.

 The yellowness of the polymer foams or foamed sheets produced in Example 9, determined according to the analysis, item 13 (see above), is shown in the following Table (11).

Table 1 1: yellowness values (Y, D1925) of the polymer foams prepared according to Example 9.

Plastisol formulation (according to Ex. 6) 2 * 3 * 4 * 5 ** 6 **

 Yellow value after 60 s [%] 22.8 23, 1 23.2 22.7 23.5 23.9

Yellow value after 90 s [%] 19.5 20 19.2 19.2 18.2 17.6

Yellow value after 120 s [%] 19, 1 16.7 18.9 15.9 14.5 16, 1 The plastisol prepared on the basis of isononyl benzoate (INB) starts with the highest yellow value of all measured plastisols, but decreases after 120 seconds residence time at 200 ° C. to the level of the plastisols according to the invention. After only 90 seconds, the plastisols which comprise the terephthalic acid esters used according to the invention are at the level of the DINP plastisol. After 120 s, significantly lower values than with the DINP are obtained, so the expansion process runs much faster. Thus, filled plastisols are provided which, despite apparent disadvantages in gelation, allow a faster processing speed and / or lower processing temperatures.

Example 10:

 Preparation of filled and pigmented expandable / foamable PVC plastisols for use in effect foams The advantages of the plastisols according to the invention based on filler and pigment-containing thermally expandable PVC plastisols, which are suitable for the production of effect foams (foams having a particular surface structure), are illustrated below. suitable. These foams are often also referred to as "boucle foams" according to the appearance pattern known from the textile sector The following plastisols according to the invention are examples of thermally expandable plastisols which are used in the production of wall coverings Example of foam layers which are used in PVC wallpaper.

The preparation of the plastisols was carried out analogously to Example 2, however, with a modified recipe. The used weights of the components for the different plastisols are shown in the following table (12). Table 12: Composition of the filled and pigmented expandable PVC plastisols from Example 10 [All data in parts by mass].

* ^* = Comparative Example ^* = according to the invention

The substances and substances used, which do not already result from the preceding examples, are explained in more detail below: Vestolit E 7012 S: emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 67; Fa. Vestolit GmbH.

 Vinnolit E 67 ST: emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 67; Fa. Vinnolit GmbH & Co. KG.

 Vinnolit EP 7060: emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 70; Fa. Vinnolit GmbH & Co. KG.

 Eastman DBT: di-n-butyl terephthalate; Plasticizer with fast gelation; Fa. Eastman Chemical Co.

Unicell D200A: azodicarbonamide; thermally activated blowing agent; Fa. Tramaco GmbH.

 Tracel OBSH 160NER: phlegmatized sulfonyl hydrazide (OBSH); thermally activated blowing agent; Fa. Tramaco GmbH.

 Microdol A1: calcium magnesium carbonate (dolomite); Filler; Fa. Omya AG.

Baerostab KK 48-1: Potassium / Zinc "kicker"; thermal propellant decomposition catalyst, reduces the substractive decomposition temperature of the blowing agent, and at the same time stabilizing action, Baerlocher GmbH.

Example 11:

Determination of the Plastisol Viscosity of the Filled and Pigmented Thermo-Expandable Plastisols from Example 10 After a Storage Period of 24 H (at 25 ° C)

The measurement of the viscosity of the plastisols prepared in Example 10 was carried out as described under analytics, item 10 (see above), using a Rheometer Physica MCR 101 (from Paar-Physica). The results are shown in the following table (13) as an example for the shear rates 100 / s, 10 / s, 1 / s and 0, 1 / s. Table 13: Shear viscosity of the plastisols from Example 10 after 24 h storage at 25 ° C.

= Comparative Example ^* = Inventive n.bb. = Not determinable

The use of the fast-gelling dibutyl terephthalate (Eastman DBT) as sole plasticizer leads to (presumably already pre-gelled at room temperature) extremely high viscosity plastisols that are clearly unworkable with conventional technological processes. The plastisols according to the invention, which contain terephthalic acid diisononyl ester mixtures together with small amounts of dibutyl terephthalate, have a significantly lower viscosity compared to the plastisol (1) based on DINP alone, which is also significantly lower than that of the higher branched terephthalic acid isononyl ester mixture (4) not according to the invention , There are thus provided plastisols according to the invention which allow a much faster processing compared to the known standard (DINP).

Example 12:

Determination of the Gelation Behavior of the Filled and Pigmented Thermally Expandable Plastisols from Example 10 The Examination of the Gelling Behavior of the Filled and Pigmented Thermosetting Plastisols Prepared in Example 10 pigmented thermally expandable plastisols, as described under analytics, point 1 1. (see above), with a Physica MCR 101 in oscillation mode after storage of the plastisols at 25 ° C for 24 h. The results are shown in Table (14) below.

Table 14: From the gelation curves (viscosity curves) certain cornerstones of the gelling behavior of the filled and pigmented expandable plastisols prepared according to Example 10.

* ^* = Comparative Example ^* = according to the invention

The special position of the dibutyl terephthalate-based plastisol is also clearly visible in the gelation curve. It already starts at room temperature at a significantly higher level (about a factor of 2) than all other plastisols considered, which indicates pre-alloying at room temperature and poor processability. With regard to the initial gelling temperature, the plastisols according to the invention are present also at the level of the standard plastisol (DINP) as with the maximum achievable final viscosity, only the speed at which the maximum plastisol viscosity is reached starting from the initial gelling temperature is slightly slower in the case of the plastisols according to the invention than that of the DINP plastisol. Thus, plastisols are made available for the production of effect foams which-with improved processing properties (see Example 11) -have substantially similar gelling properties to the current standard system and at the same time are free from ortho-phthalates. Example 13:

 Production and Evaluation of the Effect Foam from Filled and Pigmented Thermally Expandable Piastisols According to Example 10

After a storage time of about two hours, the plastisols prepared in Example 10 were foamed in a Mathis Labcoater (type LTE-TS, manufacturer: W. Mathis AG). The carrier used was a coated wallpaper paper (Ahlstrom GmbH). With the knife coater, the plastisols were applied in 3 different strengths (300pm, 200pm and 100pm). In each case 3 plastisols were spread side by side on a paper. The precoated paper thus obtained was foamed at 210 ° C for 60 seconds in the Mathis oven and gelled.

The yellow values were determined on the gelled samples as described under Analysis, Item 13 (see above). When assessing the expansion behavior, the DINP sample is used as reference standard. A normal expansion behavior (= "OK") therefore corresponds to the behavior of the DINP sample. "Foaming" results in a collapse of the foam structure, ie a poor expansion behavior is present here. In the assessment of the surface quality or the surface structure, above all, the uniformity or regularity of the surface structures is evaluated. The dimensional extent of the individual effect components is also included in the valuation.

Added to this is the assessment of the reverse side (paper) with regard to the escape or migration of recipe constituents. The grading system on which the evaluation of the surface structure is based is shown in Table (15) below. Table 15: Evaluation system for the evaluation of the surface quality of effect foams.

 Rating meaning

 1 Very good surface structure (Very high regularity and

 Uniformity of surface effects; Size of the individual effects due).

 2 Good surface texture (high regularity and uniformity of surface effects, size of single effects suitable).

 3 Satisfactory surface texture (regularity and uniformity of surface effects acceptable, size of single effects adequate).

 4 Sufficient surface texture (slight irregularities or

 Nonuniformities in the surface structure; Size of single effects slightly unbalanced).

 5 Defective surface structure (irregularities and irregularities in the surface structure, size of the individual effects unbalanced).

6 Insufficient surface texture (highly irregular and non-uniform surface effects, size of single effects inappropriate (too big / too small)). The rating system underlying the evaluation of the back page assessment (migration) is shown in the following table (16).

Table 16: Evaluation system for the backside evaluation of effect foams.

The surface structure of an effect foam (ie a foam which is to have a particular / particularly pronounced surface structuring) is determined essentially by the constituents and the processing properties of the plastisol used for the preparation. In particular, the plastisol viscosity, the flow behavior of the plastisol (eg characterized by the course of the plastisol viscosity as a function of the shear rate), the gelling behavior of the plastisol (among other things, the size and distribution of the gas bubbles), the influence of the plasticizer used on the decomposition of the blowing agent (so-called "auto-kick effects"), as well as the choice and combination of propellant (s) and decomposition to name gate (s). These are significantly influenced by the choice of starting materials and can thus be controlled in a targeted manner.

The evaluation of the back side of the coated paper allows conclusions to be drawn on the permanence of the plasticizers used and other formulation components in the gelled system. A strong migration of formulation components has many practical disadvantages besides optical and aesthetic ones. As a result, the increased stickiness leads to the adhesion of dust, which can not be removed or at least not completely removed, and thus leads to a negative appearance in a very short time. In addition, migration of formulation components usually has a strong negative impact on the printability or durability of a print. Furthermore, interactions with bonding adhesives (e.g., wallpaper adhesive) can lead to uncontrolled detachment of a wall covering.

The results of the surface and backside evaluation are summarized in Table 17.

Table 17: Results of the surface and backside evaluation of the leached effect foams from Example 13.

plastisol

(according to Ex. 10) 2 * 3 * 4 ** 5 * 6 **

 Expansion Behavior - O.K. OK. OK. OK. About Foams

Yellow value 7.3 6.6 6.7 6.5 6.8 6.3

 Rating 2 1 1 1 1 6

 Surface quality / structure

 Rating the back to 1 1 1 1 1 1

24 hours

 Rating the back to 1 2 2 1 2 1

7 days

= Comparative Example ^* = According to the invention

The expansion behavior of all samples, except for the expansion behavior of the sample containing only dibutyl terephthalate (DBT) as plasticizer, is good and equivalent to that of the DINP standard. The DBT is prone to overfoaming, so has a poor expansion behavior. The yellow value shows that significantly lower values are achieved with the plastisols according to the invention in comparison with the DINP standard, which means that the expansion proceeds significantly faster here. The evaluation of the surface structure shows the result of the expansion behavior for the DBT plastisol. As a result of the overshoot, an insufficient surface structure or premature collapse occurs. On the other hand, all plastisols according to the invention have a very good surface structure, which surprisingly even shows significant improvements compared with the DINP standard. With regard to obvious (ie visually recognizable) migration phenomena, all samples show no signs of migration after 24h storage (at 25 ° C). Even after storage for 7 days (at 25 ° C.), all effect foams according to the invention have no migration phenomena. Thus, according to the invention, plastisols and effect foams which can be produced therefrom are made available to the invention known prior art are superior or at least equivalent in optical matters, and thereby have significant advantages in the processability

Example 14:

Preparation of filled and pigmented expandable / foamable PVC plastisols for use in smooth foams

In the following, the advantages of the plastisols according to the invention on the basis of filler and pigment containing thermally expandable PVC plastisols to be illustrated, which are suitable for the production of so-called. Smooth foams (foams with a smooth surface). The following plastisols according to the invention are u.a. Exemplary for thermally expandable plastisols which are used in the production of wall coverings. In particular, the following plastisols according to the invention are exemplary of foam layers which are used in PVC wallpapers.

The preparation of the plastisols was carried out analogously to Example 2 but with a modified recipe. The weights of the components used for the different plastisols are shown in Table (18) below.

Table 18: Composition of the filled and pigmented expandable PVC plastisols from Example 14 [All data in parts by mass].

Plastisol recipe 2 * 3 * 4 ** 5 * 6 **

Vestolit E 7012 S 20 20 20 20 20 20

Vinnolit E 67 ST

17.5 17.5 17.5 17.5 17.5 17.5

Vestolit B 6021 Ultra 12.5 12.5 12.5 12.5 12.5 12.5

VESTINOL® 9 30

 Di (nonyl) terephthalate according to Ex. 1 .1 25

 Di (nonyl) terephthalate according to Ex. 1 .7 25

 Di (nonyl) terephthalate according to Ex. 1 .6 25

 Di (nonyl) terephthalate according to Ex. 1 .3 25

 Eastman DBT 5 5 5 5 30

Unicell D200A 1, 8 1, 8 1, 8 1, 8 1, 8 1, 8

Drapex 39 2.4 2.4 2.4 2.4 2.4 2.4

Kronos 2220 2.4 2.4 2.4 2.4 2.4 2.4

Microdol 1 24 24 24 24 24 24

Baerostab KK 48-1 1 1 1 1 1 1

= Comparative Example ^* = According to the invention

The substances and substances used which do not already result from the preceding examples are explained in more detail below:

Vestolit B 6021 Ultra: microsuspension PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 60; Fa. Vestolit GmbH. Drapex 39: epoxidized soybean oil; (Co) stabilizer with softening effect; Fa. Chemtura / Galata.

Example 15:

 Determination of the Plastisol Viscosity of the Filled and Pigmented Thermally Expandable Plastisols from Example 14 After a Storage Time of 24 H (at 25 ° C.)

The measurement of the viscosity of the plastisols prepared in Example 14 was carried out as described under analytics, item 10 (see above), using a Rheometer Physica MCR 101 (Paar-Physica). The results are shown in the following table (19) as an example for the shear rates 100 / s, 10 / s, 1 / s and 0, 1 / s.

Table 19: Shear viscosity of the plastisols from Example 14 after 24 h storage at 25 ° C.

* ^* = Comparative Example ^* = According to the invention n.bb. = Not determinable

All of the examples according to the invention show a significantly lower plastisol viscosity both in comparison to pure DINP (= standard) and in comparison with pure di-butyl terephthalate. The higher branched comparative example (4) also has a significantly higher plastisol viscosity, and is at high shear rates, such as they are present during processing, eg by knife coating or spraying, neither measurable nor processable. Thus, plastisols are made available that allow much better and faster processing than the current standard.

Example 16:

 Determination of the Gelling Behavior of the Filled and Pigmented Thermally Expandable Plastisols from Example 14 The investigation of the gelling behavior of the thermally filled and pigmented expandable plastisols prepared in Example 14 was carried out as described under Analytik, Item 11. (see above), with a Physica MCR 101 in oscillation mode after storage of the plastisols at 25 ° C for 24 h. The results are shown in Table (20) below.

Table 20: From the gelation curves (viscosity curves) certain cornerstones of the gelling behavior of the filled and pigmented expandable plastisols prepared according to Example 14.

plastisol

(according to example 14) 2 * 3 * 4 ** 5 * 6 **

 Achieving a Plastisolviskosi- 81 89 93 94 93 62 it

of 1, 000 Pa ^* s at [° C]

 Achieving a Plastisolviskosi- 98 120 123 123 122 66 tty

of 10,000 Pa ^* s at [° C]

 Maximum plastisol viscosity 22700 16000 14100 14200 14700 73700

[Pa ^* s]

 Temperature when reaching the 125 132 132 132 134 80 maximum plastisol viscosity

[° C]

= Comparative Example ^* = According to the invention

The pure dibutyl terephthalate-based plastisol shows, as in the effect foam formulation (see Ex. 12), clear signs of pre-gelation even at room temperature. Accordingly, despite rapid gelling at low temperatures, processability with the conventional technologies is not given. Although the plastisols according to the invention have a somewhat slower gelation at slightly elevated gelling temperatures, the maximum paste viscosity in the gelled state is achieved at a temperature similar to that of standard DINP plastisol. Thus, plastisols are provided which, with substantially improved processing properties (see Example 15), have substantially similar gelling properties to the current standard system and are at the same time ortho-phthalate free. Example 17:

 Production and Evaluation of the Smooth Foam from Thermally Expandable Piastisols According to Example 14

The smooth foams were produced analogously to the procedure described in Example 13, but using the plastisols prepared in Example 14. The evaluation of the expansion behavior was carried out analogously to the procedure described in Example 13. The yellow values were determined on the gelled samples as described under Analysis, Item 13 (see above). When assessing the surface quality or the surface structure of smooth foams, the uniformity and / or smoothness of the surface structure is evaluated above all. In addition, there is the assessment of the reverse side (paper) with regard to the escape / migration of recipe constituents. The rating system is shown in the following table (21).

Table 21: Evaluation system for the surface finish of smooth foams.

The evaluation of the backs was carried out analogously to the evaluations of effect foams (see Example 13 / Table 16). The surface structure of a smooth foam (ie a foam which is to have a smooth surface structuring), as well as the effect foam, determined essentially by the processing properties of the plastisol used for the production. In particular, the plastisol viscosity, the flow behavior of the plastisol (eg characterized by the plastisol viscosity as a function of the shear rate), the gelling behavior of the plastisol (among other things, the size and distribution of the gas bubbles), the velocity of gas bubble coalescence and the influence of the plasticizers used on the decomposition of the blowing agent (so-called "auto-kick effects"), as well as the choice and combination of blowing agent (s) and decomposition catalyst (s) due to the targeted use of surface-active substances (such as dispersing In addition, the choice of the starting materials in this case essentially influences the final result, and the evaluation of the backside of the coated paper in turn allows conclusions to be drawn regarding the permanence of the plasticizers used and other formulation ingredients in the gelled system. As already discussed, a strong migration of formulation constituents has numerous disadvantages and is generally a "knock-out criterion" for the use of the corresponding formulation.

The results of the surface evaluation are summarized in the following table (22).

Table 22: Results of the surface and backside evaluation of the leached effect foams from Example 14. plastisol

(according to example 14) 2 * 3 * 4 ** 5 * 6 **

 Expansion Behavior - O.K. OK. OK. OK. OK.

 Yellow value 8.8 8.2 8.5 8.4 8.4 8.7

 Rating 2 2 2.5 2.5 2 2

 Surface quality / structure

 Rating the back to 1 1 1 1 1 1

24 hours

 Rating the back to 7 1 2 2 2 2 1

Days.

All the examples according to the invention show an expansion behavior comparable to the DINP standard, as well as a yellow value which is consistently below the value of the DINP standard. The surface quality of the smooth foams produced is equivalent to that of the DINP standard smooth foam, as well as no migration is observed in the wallpaper paper. Thus, plastisols and foams are provided which have significantly improved properties compared to the known prior art.

Claims

claims:

1 . A foamable composition comprising at least one polymer selected from the group consisting of polyvinyl chloride, polyvinyl butyrate, polyhydroxyalkanoate, polyalkyl methacrylate, polyvinylidene chloride and copolymers thereof, a foaming agent and / or foam stabilizer and diisononyl terephthalate as plasticizer, the average degree of branching of the isononyl groups of the ester being in the range from 1.15 to 2.5.

2. Foamable composition according to claim 1, characterized in that the polymer is polyvinyl chloride.

3. Foamable composition according to claim 1, characterized in that the polymer is a copolymer of vinyl chloride with one or more monomers selected from the group consisting of vinylidene chloride, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, methyl acrylate, ethyl acrylate, or butyl acrylate.

4. Foamable composition according to one or more of claims 1 to

3, characterized in that the amount of diisononyl terephthalate is 5 to 120 parts by mass per 100 parts by mass of polymer.

5. Foamable composition according to one or more of claims 1 to

4, characterized in that additional plasticizers other than diisononyl terephthalate are additionally contained in the foamable composition.

6. Foamable composition according to one or more of claims 1 to

5, characterized in that the composition contains a gas bubble developing component as a foaming agent and optionally a kicker.

7. Foamable composition according to one or more of claims 1 to

6, characterized in that the composition contains microsuspension and / or emulsion PVC.

8. Foamable composition according to one or more of claims 1 to

7, characterized in that the composition contains further constituents selected from the group consisting of fillers, pigments, matting agents, heat stabilizers, costabilizers, antioxidants, viscosity regulators, foam stabilizers, process aids and lubricants.

9. Use of the foamable composition according to claims 1 to 8 for floor coverings, wallpaper or artificial leather.

10. Foamed molded article containing the foamable composition according to claims 1 to 8.

1 1. Floor covering containing the foamable composition in the foamed state according to claims 1 to 8.

12. wall wallpaper containing the foamable composition in the foamed state according to claims 1 to 8.

13. Synthetic leather containing the foamable composition in the foamed state according to claims 1 to 8.