EP2643399A1

EP2643399A1 - Use of di(isononyl)cyclohexanoate (dinch) in expandable pvc formulations

Info

Publication number: EP2643399A1
Application number: EP11788081.5A
Authority: EP
Inventors: Hinnerk Gordon Becker; Michael Grass; Andre Huber
Original assignee: Evonik Oxeno GmbH and Co KG
Current assignee: Evonik Operations GmbH
Priority date: 2010-11-24
Filing date: 2011-10-31
Publication date: 2013-10-02
Also published as: CN103221468A; JP5859018B2; RU2013128416A; CA2817868A1; CN103221468B; SG190844A1; MX2013005509A; JP2013543920A; RU2608410C2; DE102010061867A1; WO2012069286A1; US20130310471A1; KR20130117823A

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 (meth)acrylate, and copolymers thereof, an expanding agent and/or foam stabilizer, and 1,2-cyclohexane dicarboxylic acid diisononyl ester as a plasticizer. The invention further relates to expanded molded articles and the use of the expandable composition for floor coverings, wallpapers, or synthetic leather.

Description

Use of di (isononyl) cyclohexanoic acid ester (DINCH) in foamable PVC formulations

The invention relates to a foamable composition comprising at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and diisononyl-1, 2-cyclohexandicarbonsäureester as a 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).

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) such as BBP (benzyl-butyl-phthalate) are used at least proportionally in the formulation. In many cases, however, the sole use of DINP is also established for cost reasons. In connection with the discussion about ortho-phthalates in children's toys, various legal measures have been adopted to regulate this substance group. and further tightening can not be ruled out in principle. Thus, the industry is working intensively on the development of new ortho-phthalate-free plasticizers, which are toxicologically safe and in their technical properties equal to the phthalates. For example, terephthalic acid esters such as di-2-ethylhexyl terephthalate (DEHT) or diisononyl-1,2-cyclohexanedicarboxylic acid ester (DINCH) have recently been discussed as possible alternatives.

EP 1 505 104 describes a foamable composition which contains isononyl benzoate as plasticizer. The use of benzoic acid isonon esters as plasticizers, however, has the considerable disadvantage that isononyl benzoate are very volatile and therefore escape from the polymer during processing and also with increasing storage and use time. This provides considerable problems, in particular in applications, for example indoors. Therefore, in the prior art, the isononyl benzoates are frequently used as plasticizer blends with conventional other plasticizers, for example phthalic acid esters. Isononyl benzoates are also known as

Fast gelator used. Furthermore, the use of rapid gellants such as BBP or also benzoic isononyl ester would cause an excessive increase in the viscosity of the corresponding plastisol with time.

Other plasticizers known in the prior art include terephthalic acid alkyl esters for use in PVC. For example, 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 also described 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. can be used. But even these plasticizers are classified as relatively volatile fast gelators, so that the above problems persist in principle.

WO 2006/136471 A1 describes mixtures of diisononyl esters of 1,2-cyclohexanedicarboxylic acid and processes for their preparation. Mixtures of diisononyl esters of 1,2-cyclohexanedicarboxylic acid are characterized by a certain average degree of branching of the isononyl radicals, which is in the range from 1.2 to 2.0. The compounds are used as plasticizers for PVC. Furthermore, WO 03/029339 numerous applications of tests on Cyclohexandicarbonsäureestern, including DINCH, presented.

In WO 2009/085453 it is stated that DINCH has significantly poorer gelling properties than, for example, DINP, and that fast gelators must be used for compensation.

None of the above documents has data on the behavior of DINCH in foamed formulations. However, it can be assumed that the significantly poorer gelation behavior of DINCH compared to DINP negative impact on the foaming availability, ie the percentage foaming per unit time at a given temperature will affect. This is also from a statement in the well-known text book "Handbook of Vinyl Formulating", Second Edition, Publisher John Wiley (ISBN 978-0-471 -71046-2), p. 384, to conclude that namely ("... with slower fusing plasticizers. "). poorly gelling plasticizers require higher temperatures for foaming. Higher temperatures, however, are disadvantageous for the processor, on the one hand the energy costs increase and on the other hand the product is discolored by thermal aging. Thus, the object of the invention is to identify such plasticizers, which show even without the use of Schnellgelierern foaming properties that are equal to those of the DINP and therefore the above difficulties of faster viscosity increase of the corresponding plastisols with time (storage stability) and the significantly higher volatility no longer shows. Likewise, these plastisols should also be easy to process, ie exhibit a viscosity which does not exceed the market standard DINP, because otherwise the viscosity of the plastisol would have to be adjusted by increased addition of diluents and then the thinner would have to be thermally expelled again during processing.

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 (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and diisononyl-1, 2-cyclohexandicarbonsäureester as plasticizers.

It has surprisingly been found that compositions containing diisononyl-1, 2-cyclohexanedicarboxylic acid esters (DINCH) and a foaming agent or foam stabilizer are suitable for the production of foams or foamed layers, compared to corresponding DINP-containing compositions at the same temperature and residence time show much stronger expansion behavior, although the gelling speed is reduced. This makes it possible to lower either the processing temperature or lower the residence time at the same temperature, resulting in a higher and thus advantageous for the processor product output per unit time. This is surprising inasmuch as this contradicts the common textbook opinion (eg, "Handbook of Vinyl Formulating", Second Edition, John Wiley Publishing (ISBN 978-0-471 -71046-2), page 384) that more gelling plasticisers too higher expansion rates in foaming, stands. Furthermore, the composition according to the invention leads to a lower plastisol viscosity, in particular in the technically important range of higher shear rates. This has the consequence, for example, that even with the addition of solid additives, the viscosity still lies in areas in which the foamable compositions can be processed without having to add additional expensive viscosity-reducing substances. 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 increase productivity.

Another advantage is that the foamable compositions can be processed at lower temperatures and therefore also have a much lower yellow value. Even at the same processing temperature of the yellow value of the corresponding foam sheets of the compositions of the invention is lower than that of a corresponding DINP recipe.

Furthermore, it should be noted that the diisononyl-1,2-cyclohexanedicarboxylic acid esters according to the invention are significantly less volatile than isononyl benzoates which are used in the prior art in foamable compositions. The possibility of eliminating volatile fast gelling agents also facilitates the use for interior applications since the plasticizers of the composition according to the invention are less volatile and less readily escape from the plastic. At least one polymer contained in the foamable composition is selected from the group consisting of polyvinyl chloride (PVC), polyvinylidene chloride, polyalkyl (meth) acrylate (PAMA) and polyvinyl butyrate (PVB).

In a 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 butyrate, methyl acrylate, ethyl acrylate or butyl acrylate. Preferably, the amount of diisononyl-1,2-cyclohexanedicarboxylic acid ester in the foamable composition is 5 to 150 parts by mass, preferably 10 to 100 parts by mass, more preferably 10 to 80 parts by mass, and most preferably 15 to 90 parts by mass per 100 parts by mass Polymer.

The foamable composition may optionally contain additional additional plasticizers, other than diisononyl-1,2-cyclohexanedicarboxylic acid esters.

The solvation and / or gelling ability of the additional plasticizers may in this case be higher, equal to or lower than those of the diisononyl-1, 2-cyclohexanedicarboxylic acid esters according to the invention. The mass ratio of the additional plasticizers used to the diisononyl-1, 2-cyclohexanedicarboxylic acid esters used according to the invention is in particular between 1:10 and 10: 1, preferably between 1:10 and 8: 1, more preferably between 1:10 and 5: 1 and in particular preferably between 1:10 and 1: 1.

In particular, the additional plasticizers are esters of orthophthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (excluding diisononyl-1,2-cyclohexanedicarboxylic acid ester), trimellitic acid, citric acid, benzoic acid, isononanoic acid, 2-ethylhexanoic acid , the octanoic acid, 3,5,5-trimethylhexanoic acid and / or esters of butanol, pentanol, octanol, 2-ethylhexanol, isononanol, decanol, dodecanol, tridecanol, glycerol and / or isosorbide and their derivatives and mixtures , Preferably, citric acid esters such as acetyl tributyl citrate or benzoates can be used.

In principle, the foamable composition can be foamed chemically or mechanically. In this context, chemical foaming is understood to mean that the foamable composition contains a foaming agent which is oxidized by mix decomposition at higher temperature forms gaseous components, which then cause the foaming.

It is therefore further preferred that the foamable composition according to the invention contains a foaming agent. This foaming agent may be a gas bubble developing compound optionally containing a kicker. As such Kicker metal compounds are called, which catalyze the thermal decomposition of the gas bubbles developing component and cause the foaming agent decomposes to gas evolution and the foamable composition is foamed. Foaming agents are also referred to as blowing agents. The gas-bubble-developing component used is preferably a compound which decomposes into gaseous constituents under the influence of heat and thus causes the composition to expand. A typical representative of such compounds is z. As azodicarbonamide, which releases mainly thermal decomposition N ₂ and CO. The decomposition temperature of the propellant can be reduced by the kicker.

Another usable blowing agent is p, p ^'oxybis (benzenesulfonhydrazide), also known as OBSH. This is characterized by a lower compared to azodicarbonamide decomposition temperature. Further information on propellants can be found in the "Handbook of Vinyl Formulating", Second Edition, John Wiley Publication (ISBN 978-0-471 -71046-2), pages 379. The most preferred blowing agent is azodicarbonamide.

In contrast to chemical foaming, the foam is produced by mechanical foaming in that a gas, preferably air, is introduced into the composition by vigorous stirring, similar to the production of whipped cream (so-called whipped foam). The foam is then applied, for example, to a support and then fixed by the high processing temperature. In order to prevent the disintegration of the foam bubbles over time, foam stabilizers are preferably used in mechanical foams. Commercially available foam stabilizers may be present in the composition according to the invention as foam stabilizers. Such foam stabilizers can be based, for example, on silicone or soap For example, under the brand name BYK (Byk-Chemie) offered. These are used in amounts of 1 to 10, preferably 1 to 8, particularly preferably 2 to 4 parts by mass per 100 parts by mass of polymer. Further details on foam stabilizers which can be used (for example calcium dodecylbenzenesulfonate) are mentioned, for example, in DE 10026234 C1.

In principle, the foamable compositions according to the invention can be, for example, plastisols which can be prepared by mixing emulsion or microsuspension PVC with liquid components such as plasticizers.

It is further preferred that the foamable composition contains an emulsion PVC. Most preferably, the foamable composition according to the invention comprises an emulsion PVC which has a molecular weight expressed as K value (Fikent's constant) of 60 to 95 and more preferably of 65 to 90.

The foamable composition may furthermore preferably comprise additional additives which are in particular selected from the group consisting of fillers, pigments, heat stabilizers, antioxidants, viscosity regulators, (further) foam stabilizers, flame retardants, adhesion promoters and lubricants.

The thermal stabilizers neutralize, for example, during and / or after the processing of the PVC split off hydrochloric acid and prevent thermal degradation of the polymer. Suitable thermal stabilizers are all customary PVC stabilizers in solid and liquid form, for example based on Ca / Zn, Ba / Zn, Pb, Sn or organic compounds (OBS), and also 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 to thermal stabilizers. As pigments, both inorganic and organic pigments can be used in the context of the present invention. The content of pigments is between 0.01 to 10 mass%, preferably 0.05 to 5 mass%, particularly preferably 0, 1 to 3 mass% per 100 mass parts of polymer. Examples of inorganic pigments are CdS, COO / Al ₂ O 3, Cr ₂ O 3. Known organic pigments are, for example, azo dyes, phthalocyanine pigments, dioxazine pigments and aniline pigments.

Aliphatic or aromatic hydrocarbons, but also carboxylic acid derivatives such as, for example, the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate known as TXIB (Eastman) can be used as viscosity-reducing reagents. The latter can also be easily substituted by benzoic acid isonononyl esters due to their similar intrinsic viscosity. Due to the low viscosity of plastisols based on the composition according to the invention, the consumption of viscosity-reducing reagents is rather low. Viscosity reducing reagents are added in proportions of 0.5 to 30, preferably 1 to 20, more preferably 2 to 15 parts by mass per 100 parts by mass of polymer. Special viscosity-lowering additives are offered, for example, under the trade name Viskobyk (Byk-Chemie).

A further subject of the present application is the use of the foamable composition for floor coverings, wallpaper or artificial leather. In addition, a further subject of the invention is a floor covering containing the foamable composition according to the invention, a wall-covering comprising the foamable composition according to the invention or synthetic leather containing the foamable composition according to the invention.

The diisononyl-1, 2-cyclohexandicarbonsäureester are prepared, for example, as described in WO 2006/136471 A1. The preparation of these esters can be carried out by transesterification of esters of 1, 2-cyclohexanedicarboxylic acid with a mixture of isomeric primary nonanols. The diisononyl-1, 2-cyclohexanedicarboxylic acid ester may also be obtained by esterification of 1, 2-cyclohexanedicarboxylic acid or the corresponding anhydride with a mixture of primary nona be prepared nole. Also preferably, a reaction sequence containing a Diels-Alder reaction of butadiene and maleic anhydride can be used to prepare the diisononyl-1,2-cyclohexanedicarboxylic acid ester, as described for example in WO02 / 066412. The diisononyl-1, 2-cyclohexanedicarboxylic acid esters can also be produced by ring hydrogenation of the corresponding diisononyl phthalates.

For example, for the preparation of the diisononyl-1,2-cyclohexanedicarboxylic acid esters, particularly suitable nonanol mixtures from Evonik Oxeno are available on the market. Furthermore, diisononyl-1, 2-cyclohexanedicarboxylic acid ester (DINCH) can also be obtained as a commercial product from BASF (HEXAMOLL DINCH) or various Asian companies such as NanYa, Taiwan.

The diisononyl-1, 2-cyclohexanedicarboxylic acid esters used according to the invention are characterized as follows in terms of their thermal properties (determined by differential calorimetry / DSC):

1 . They have at least one glass transition point in the first heating curve (heating rate 10 K / min.) Of the DSC thermogram.

2. At least one of the glass transition points detected in the aforementioned DSC measurement is below a temperature of -80 ° C, preferably below -85 ° C, more preferably below -88 ° C, and most preferably below -90 ° 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 -85 ° C., preferably below -88 ° C., and especially preferably below -90 ° C.

3. In the first heating curve (heating rate 10 K / min.) Of the DSC thermogram you have no detectable melting signal (and thus a melting enthalpy of 0 J / g). The glass transition temperature and, to a certain extent, 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 preparation of the foamable composition according to the invention can be carried out in various ways known to the person skilled in the art. In general, however, the composition is prepared by intensive mixing of all components in a suitable mixing container. Here, the components are preferably added sequentially (see also E.J. Wickson, "Handbook of PVC Formulating", John Wiley and Sons, 1993, p. 727).

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

Such foamed products are, for example, imitation leather, floors or wall-mounted wallpaper, in particular the use of the foamed products in cushion vinyl floors and wallpapers.

The foamed products of the foamable composition according to the invention are prepared by first applying the foamable composition to a support or another polymer layer and foaming the composition before or after application, and finally thermally applying the applied and / or foamed composition is processed.

In contrast to the mechanical foam, in the case of chemical foams, the foam is formed only during processing, as a rule in a gelling channel, ie, the unfoamed composition is applied to the carrier, preferably by brushing. In this embodiment of the method, a professional lation of the foam can be achieved by selective application of inhibitor solutions, for example via a rotary screen printing machine. At the sites where the inhibitor solution was applied, expansion of the plastisol during processing either does not take place at all or only delayed. In practice, chemical foaming is used to a much greater extent than mechanical ones. For more information on chemical and mechanical foaming, see, for example, EJ Wickson, Handbook of PVC Formulating, 1993, John Wiley & Sons. Optionally, profiling can also be achieved subsequently by means of the so-called mechanical embossing, for example by means of an embossing roller.

In both processes, such materials can be used as the support which remain firmly bonded to the foam produced, such as 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 be, for example, metal bands 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. In chemical foaming, the gelling channel can be combined with a device used to produce the foam, for example, it is possible to use only one gelling channel, with the front one in the front Part at a first temperature by decomposition of a gas-forming component, the foam is chemically generated and this foam in the rear part of the gelation at a second temperature, which is preferably higher than the first temperature, is transferred to the semifinished product or final product It also possible that gelation and Foaming takes place at the same time 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 said gelling temperatures for a period of 0.5 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 180 to 220 ° 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 according to the invention have the advantage over the prior art that they can be processed either at the same temperatures faster or alternatively at lower temperatures, and thus the efficiency of the production process of the PVC foams is considerably improved. Furthermore, the plasticizers used in the PVC foam are less volatile than, for example, the benzoic acid isononyl esters mentioned in the prior art, and thus the PVC foam is particularly suitable in particular for interior applications.

The following examples are intended to explain the invention in more detail. 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: 20m, 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: ° 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 done manually against existing reference substances, the indication of the purity is 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. 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 device used and closing heated with 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 melting enthalpy is determined by integration of the peak area (s) by means of device software.

3. 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 homogenized again in the batch tank by stirring with a spatula, then filled into the measuring system and measured isothermally at 25 ° C. During the measurement the following points were activated: 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 shear rate down ramp, starting at 200 s ^"1 and ending at 0, 1 s ^{" 1} , divided into a logarithmic series with 30 steps each with a 5 second measurement point duration.

The measurements were usually carried out (unless stated otherwise) after storage / maturation of the plastisols of 24 h. Between measurements, the plastisols were stored at 25 ° C.

4. 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 device to achieve the best possible heat distribution. Measurement parameters:

Mode: temperature gradient (temperature ramp linear)

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

no automatic gap tracking

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, by means of a tangent method, the maximum plastisol viscosity achieved in the present experimental setup was determined, and by precipitating a solder, the temperature at which the maximum plastisol viscosity occurs. 5. Preparation of the foam films and determination of the expansion rate

The foaming behavior was determined with the aid of a thickness cutter suitable for soft PVC measurements (KXL047, Mitutoyo) with an accuracy of 0.01 mm 5. For the film production, the roll doctor of a Mathis Labcoaters (type:

LTE-TS; Manufacturer: Fa. W. Mathis AG) set a doctor gap of 1 mm. 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 foaming, a gelled and unfoamed film was first produced at 200 ° C./30 seconds dwell time. 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.

15 Subsequently, the foamed foils (foams) were also produced with the Mathis-Labcoater at 4 different oven residence times (60s, 90s, 120s and 150s). After cooling the foams, the thicknesses were also measured at three different locations. The mean of the thicknesses and the initial thickness were needed to calculate the expansion. (Example: (foam thickness-20 initial thickness) / initial thickness ^* 100% = expansion).

6. 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 of interest in two respects. 25 On the one hand it indicates the degree of decomposition of the propellant (= yellow in the undecomposed state), on the other hand it is a measure of the thermal stability (discoloration due to thermal stress). The color measurement of the foam films was carried out with a Spectro Guide from the Byk-Gardner company. The background for the color measurements was a white reference tile. 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.

Examples: Example 1

Preparation of expandable / foamable PVC plastisols containing the diisononyl-1,2-cyclohexanedicarboxylic acid esters used according to the invention (using filler and pigment)

In the following, the advantages of the plastisols according to the invention are to be clarified on the basis of a filler and pigment-containing thermally expandable PVC plastisol. The following plastisols according to the invention are u.a. Exemplary for 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 printable and / or inhibitable top foams in multilayer PVC floors.

The used weights of the components for the different plastisols are shown in the following table (1). 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 circular Dissolver VDKV30-3 (manufacturer: Niemann). The mixing cup 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 readout of the thermocouple reached 30.0 ° C. (temperature increase as a result of the friction energy / energy dissipation, see, for example, 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.

Table 1: Composition of the filled and pigmented expandable PVC plastisols according to Example 1. [All data in phr (= parts by mass per 100 parts by mass of PVC)]

= Comparative Example ^* = According to the invention

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

VESTOLIT P1352 K: emulsion PVC (homopolymer) with a K value (determined in accordance with DIN EN ISO 1628-2) of 68; Fa. Vestolit GmbH Hexamoll DINCH: di-isononyl-1,2-cyclohexanedicarboxylate; BASF SE, ester content by GC (see analysis point 1)>99.9%; Glass transition temperature T _G = -91 ° C. (measurement according to analytic point 2)

VESTINOL® 9: diisononyl (ortho) phthalate (DINP), plasticizer; Evonik Oxeno GmbH, ester content by GC (see analysis point 1)>99.9%; Glass transition temperature T _G = -86 ° C. (measurement according to analytic point 2)

Unifoam AZ Ultra 1035: azodicarbonamide; thermally activated blowing agent; Fa. Hebron S.A.

Calcilit 8G: calcium carbonate; Filler; Fa. Alpha Calcite

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)

Zinc oxide active ^® : ZnO; Thermal decomposition catalyst ("kicker") for reducing the substractive decomposition temperature of the blowing agent, and also acting as a stabilizer: for better distribution, the zinc oxide was treated with the corresponding plasticizer (mass ratio 1: 2) and rubbed on a 3-roll mill; Lanxess AG Example 2:

Determination of the Plastisolviskosität of the filled and pigmented thermally expandable Piastisole from example 1 after a storage period of 24 h (at 25 ° C) The measurement of the viscosities of the plastisols prepared in Example 1 was carried out as described in analytics, point 3. (see above), with a Rheometer Physica MCR 101 (Paar-Physica). The results are shown in the following table (2) as an example for the shear rates 200 / s and 14.5 / s. Table 2: Shear viscosity of the plastisols from Example 1 after 24 h storage at 25 ° C.

= Comparative Example ^* = According to the invention

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 improved processing properties, in particular to a considerably increased coating speed during coating and / or doctor application.

Thus, according to the invention, plastisols are provided which have similar or significantly improved processing properties over plastisols which are based on the standard plasticizer DINP.

Example 3:

Determination of the gelling behavior of the filled and pigmented thermally expandable plastisols from Example 1

Examination of the gelling behavior of the filled and pigmented thermo-expandable plastisols prepared in Example 1 was carried out as described under Analysis, Item 4 (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 the following Table (3). Table 3: From the gelation curves (viscosity curves) certain cornerstones of the gelling behavior of the filled and pigmented expandable plastisols prepared according to Example 1

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

Example 4:

Preparation of the foam films and determination of the expansion or foaming behavior of the thermo-expandable plastisols prepared in Example 1 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 analytics, item 5, however, using the filled and pigmented plastisols prepared in Example 1. The results are shown in Table (4) below. Table 4: Expansion of the polymer foams or foam foils produced from the filled and pigmented thermally expandable plastisols (according to Ex. 1) at different furnace residence times in the Mathis Labcoater (at 200 ° C.)

With the plastisols containing the diisononyl-1, 2-cyclohexanedicarboxylates used according to the invention, higher foam heights or expansion rates are achieved after a residence time of 120 and 150 seconds in comparison with the current standard plasticizer DINP. There are thus provided thermally expandable plastisols with fillers which despite apparent disadvantages in gelling behavior (see Example 3) have advantages in thermal expandability. In the case of plastisols with fillers, the completeness of the decomposition of the blowing agent used, and thus the progress of the expansion process, can also be read off from the color of the foam produced (despite the content of white pigment). The lower the yellowing of the foam, the further the expansion process is completed. The yellowness value of the polymer foams or foam foils prepared in Example 4, determined according to the analysis, item 6 (see above), is shown in the following Table (5). Table 5: Yellowness values (Y, D1925) of the polymer foams prepared according to Example 4

The plastisols prepared on the basis of the composition according to the invention have a lower color number.

Thus, filled plastisols are provided which, despite apparent disadvantages in gelation, allow a faster processing speed and / or lower processing temperatures with improved yellowness.

Example 5:

Production and testing of expandable / foamable PVC plastisols containing the diisononyl-1,2-cyclohexanedicarboxylic acid esters used according to the invention (with variation of the filler content)

To further underline the breadth of the invention, in another series using a different type of PVC, the amounts of filler (here, chalk) from 0, ie, unfilled, but pigmented system, are varied to 133 phr, ie, high-filled formulation , The production of the plastisols and the foams produced therefrom as well as the determination of the expansion rate and the yellowness values were carried out analogously to the above examples. Table 6: Recipes

Vestolit E 7012 S: emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 67; Fa. Vestolit GmbH

Calibrite OG: mineral filler (calcium carbonate); Fa. Omya AG

All other recipe components were already described in detail in the first example. From the o.a. By way of example, the thickness of the foamed film was determined in each case and the expansion rate in percent was calculated therefrom (see Analysis, Point 5).

Table 7: Expansion of the filled and pigmented thermally expandable plastisols (according to Ex. 5) at different furnace residence times in the Mathis Labcoater (at 200 ° C) produced polymer foams or foam foils (All data on emission rates in percent)

From the examples listed in Table 7, it should be clearly understood that the foaming behavior of compositions containing DINCH (E1 to E5), expressed by the% expansion rates, can be assessed consistently better than the comparable compositions with the plasticizer DINP (state of the art) Technique, V1 to V5).

This statement is further emphasized by the yellowness indices obtainable with the compositions according to the invention.

Table 8: Yellowness of the foamed sheets obtained

All information on Yl values are dimensionless Thus it could be shown that significantly better results are achieved when using the compositions according to the invention. It is surprising that despite the poorer gelling behavior, DINCH shows these effects in contrast to the usual textbook opinion.

Example 6 (wallpaper foam)

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 1 but with a modified recipe. The weights of the components used for the different plastisols are shown in Table 9 below (all data in phr (= parts by mass per 100 parts by mass of PVC)).

Table 9 recipes

* = according to the invention; ** = Comparative Example The substances and substances used are explained in more detail below, unless they have already been mentioned in one of the earlier examples.

Microdol A1: mineral filler; Fa. Omya AG

Baerostab KK 48: potassium / zinc kicker; Fa. Baerlocher GmbH

Isopar J: isoparaffin, cosolvent to lower plastisol viscosity; Fa. Möller Chemie.

Example 7:

Production and evaluation of the effect foam from filled and pigmented thermally expandable plastisols

After a storage time of about two hours, the plastisols prepared in Example 6 were foamed in a Mathis Labcoater (type LTE-TS, manufacturer: W. Mathis AG). The carrier used was a coated wallpaper paper (Ahlstrom GmbH). The paper was placed in a tenter and dried at 200 or 210 ° C for 10 seconds prior to coating. With the Rakelbe- coating unit, the plastisols were applied in 3 different thicknesses (300, 200 and 10 μm). In each case 3 plastisols were spread side by side on a paper. The excess plastisol was removed from the backing paper. The gelation was carried out at 200 ° C and at 210 ° C for 60 seconds in the Mathis oven

The yellow values were determined on the gelled samples as described under Analysis, Item 6 (see above).

The yellow values obtained are listed in the following table:

Table 10: Yellowness of boucle foams:

All information on Yl values are dimensionless

In both cases, a significantly lower yellowness was achieved with the plastisol according to the invention.

When assessing the expansion behavior, the DINP sample (A) is used as a reference standard.

The foams processed at 200 ° C each show a good expansion behavior. At 210 ° C, however, the comparison sample is overgrown, here the foam has already broken down again. Thus, there is a poor expansion behavior here. With the plastisol according to the invention a good expansion behavior could be found even at 210 ° C. Thus, it can be concluded that there is an advantage here because of the larger work window.

In the assessment of the surface quality or the surface structure, above all, the uniformity or regularity of the surface structures is evaluated. Also the dimen- The size of the individual effect components is included in the valuation.

The grading system on which the evaluation of the surface structure is based is shown in the following Table (1 1).

Table 1 1: Evaluation system for the evaluation of the surface quality of effect foams.

The surface structure of the foams obtained was evaluated by means of the scheme given in Table 11. The results are listed in the following table (12):

Table 12: Evaluation of the surface structure of the corresponding boucle foams

The foamable composition of the invention shows significant advantages over the previous industry standard DINP

The numerous examples cited have impressively demonstrated that the compositions according to the invention containing DINCH show significant advantages. Due to the poorer gelling behavior of DINCH compared to DINP this could not be predicted. Therefore, this result is surprising and based on an inventive step.

Claims

claims:

1 . Foamable composition comprising at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and diisononyl-1, 2-cyclohexandicarbonsäureester as plasticizer.

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, Vinylbuty- rat, 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-1, 2-cyclohexandicarbonsäureester is 5 to 150 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 in addition further plasticizers except diisononyl-1, 2-cyclohexandicarbonsäureester are included 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 emulsion PVC.

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

7, characterized in that the composition comprises additives selected from the group consisting of fillers, pigments, thermal stabilizers, antioxidants, viscosity regulators, foam stabilizers 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.