EP2094750A1

EP2094750A1 - Process for producing improved binders for plastisols

Info

Publication number: EP2094750A1
Application number: EP07819940A
Authority: EP
Inventors: Jan Hendrik Schattka; Gerd LÖHDEN; Winfried Belzner; Ulrike Behrens; Christian Golditz; Sebastian Grimm; Herbert Jung; Florian Matthess
Original assignee: Evonik Roehm GmbH
Current assignee: Roehm GmbH Darmstadt
Priority date: 2006-11-22
Filing date: 2007-08-15
Publication date: 2009-09-02
Also published as: DE102006057145A1; KR20090082413A; CA2666381A1; TW200837118A; BRPI0719301A2; JP2008127560A; WO2008061812A1; US20100062271A1; RU2009123369A

Abstract

The invention relates to a process for producing binders for plastisols which ensures a constant, high product quality over a large number of batches. The binders obtained from this process make it possible to formulate plastisols which have improved storage stability and, after gellation, improved mechanical properties.

Description

Process for the preparation of improved binders for

plastisols

The invention relates to an improved process for the preparation of copolymers which are used as binders in Plastisolformulierungen.

Among plastisols are generally dispersions of finely divided

Plastic powders understood in plasticizers, which when heated to higher

Gelling temperatures, i. Harden.

Plastisol: By "plastisols" is meant herein mixtures which consist of at least one binder and one plasticizer. In addition, plastisols may e.g. further binders, further plasticizers, fillers, rheology aids, stabilizers, adhesion promoters, pigments and / or blowing agents.

Primary particles: By "primary particles" is meant herein the particles present after emulsion polymerization in the resulting dispersion (latex).

Secondary Particles: By "secondary particles" is meant herein the particles obtained by drying the dispersions (latexes) obtained in the emulsion polymerization.

(Meth) acrylates: By this notation is meant herein both the esters of methacrylic acid (such as methyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate) and the esters of acrylic acid.

Particle Size When referring to particle size, average particle size, or average particle size is, unless expressly stated otherwise, the volume-weighted average particle size distribution meant, as can be obtained for example by laser diffraction (such as with the aid of a Coulter LS 13 320, manufacturer Beckmann-Coulter).

Such - sometimes referred to as "organosols" - plastisols are used for a variety of purposes, in particular as a sealant and sound insulation, automotive underbody protection, as corrosion protection coatings for metals, as a coating of sheet metal strips (coil coating), for impregnation and coating of substrates made of textile materials and paper (also eg carpet backing coatings), as floor coatings, as final coatings for floor coatings, for artificial leather, as cable insulation and much more.

An important application of plastisols is the protection of body panels on the underbody of motor vehicles against stone chipping. In this application, particularly high demands are placed on the plastisol pastes and the gelled films.

Naturally, a high mechanical resistance to abrasion caused by rockfall is essential. Furthermore, as long as possible usability of plastisol pastes (storage stability) is also essential in the automotive industry.

The plastisol pastes must not tend to absorb water, because before the gelation absorbed water evaporates at high temperatures during gelation and leads to undesirable bubble formation.

Furthermore, the plastisol films have a good adhesion to the substrate (usually KTL sheet), which is not only an important prerequisite for the abrasion properties, but also essential for corrosion protection.

By far the most widely used plastic by far for the production of plastisols is polyvinyl chloride (PVC). Plastisols based on PVC show good properties and are also relatively cheap, which is one of the main reasons for their still widespread use.

However, a number of problems arise in the production and use of PVC plastisols. Even the production of PVC itself is not unproblematic, because in the production facilities the workers there are exposed to a health hazard due to the monomeric vinyl chloride. Residues of monomeric vinyl chloride in the PVC could also be hazardous to health during further processing or at the end consumers, although the contents are generally only in the ppb range.

Particularly serious in the use of PVC plastisols that the PVC is both heat and light-sensitive and tends to elimination of hydrogen chloride. This is a serious problem especially when the plastisol has to be heated to a higher temperature, since the hydrogen chloride released under these conditions has a corrosive effect and attacks metallic substrates. This is of particular importance when relatively high stoving temperatures are used to shorten the gel time, or when, as in spot welding, locally high temperatures occur.

The biggest problem arises with the disposal of waste containing PVC: in addition to hydrogen chloride, dioxins may be produced, which are highly toxic. In combination with steel scrap, PVC residues can lead to an increase in the chloride content of the molten steel, which is also disadvantageous.

For the reasons mentioned, alternatives to PVC plastisols have long been sought and developed, which have their good processing and end properties, but do not have the problems associated with the chlorine contained.

So z. B. proposed to at least partially replace vinyl chloride polymers by acrylic polymers (JP 60 258241, JP 61 185518, JP 61 207418). However, this approach has only reduced but not solved the chlorine-related problems.

Various polymers - usually but not exclusively prepared by emulsion polymerization - have been studied as chlorine-free binders; including eg Polystyrene copolymers (eg DE 4034725) and polyolefins (eg DE 10048055). With regard to their processability and / or the properties of the pastes or of the gelled films, however, such plastisols do not meet the demands made by users on the basis of many years of experience with PVC plastisols.

However, a good alternative to PVC are poly (meth) acrylates which have been described for many years for the preparation of plastisols (for example DE 2543542, DE 3139090, DE 2722752, DE 2454235).

In recent years, plastisols based on polyalkyl (meth) acrylates have been the subject of numerous patent applications which have brought improvements in the various properties required.

Various patents cite the possibility of improving adhesion by incorporation of certain monomers.

These may be, for example, nitrogen-containing monomers, e.g. in DE 4030080. DE 4130834 describes a plastisol system with improved adhesion to cataphoresis sheet based on polyacrylic (meth) acrylates, wherein the binder contains an acid anhydride in addition to monomers having an alkyl substituent of 2-12 carbon atoms.

The improvement in the adhesion of such monomers is generally not very strong and yet to achieve a significant improvement in adhesion, correspondingly high levels of these monomers must be used. This, in turn, also affects other properties of the plastisol, such as storage stability or plasticizer capacity.

When changing the monomer composition, one often faces the dilemma of having to accept the deterioration of another for the improvement of one property.

In addition, there have been numerous attempts to achieve adhesion not by the binder itself but by various adhesion promoters added during formulation of the plastisol. The most important such adhesion promoters are blocked isocyanates, which are usually used in conjunction with amine derivatives as curing agents (examples mentioned are EP 214495, DE 3442646, DE 3913807).

The use of blocked isocyanates is now widespread and undoubtedly contributes significantly to the adhesion of plastisol films. Nonetheless, inadequate adhesion remains a problem with these primers. In addition, these additives are quite expensive, which is why an economical use is preferable.

There are also a number of other proposed solutions, of which the use of Sacchahden as adhesion promoter should be mentioned here (DE 10130888).

The achievement of sufficient adhesion of plastisol films on different substrates is still a problem, despite all efforts and approaches, which arises in the development of plastisols for certain applications.

As already mentioned, storage stability is another important property of plastisols.

It is known that the storage stability increases with increasing size of the primary particles. As early as 1974, Teroson GmbH (DE 2454235) mentions in an application that the storage stability is too low if the particle size is too small. In this document, a relationship is established and explained between the required particle size and the glass transition temperature of the particles.

Meanwhile, the greatest agreement among experts is that the emulsion polymerization is particularly suitable for the preparation of binders for plastisols.

Although the production of large particles by the emulsion polymerization is in principle possible. However, very large particles lead to problems which must be taken into account. Thus, in the preparation of the very careful and precise work must be done in order to achieve the desired particle size and to achieve reproducible. This usually requires an extension of the Polymerization process, which is economically detrimental in industrial production.

Small changes, as they can not always be prevented with reasonable effort - such as fluctuations in the dosing speed - can lead to fluctuations in the particle size, and thus to fluctuations in product quality despite attentive attention.

Especially in the widespread production of Plastisolbindemitteln by emulsion polymerization by the batch or semi-batch process, this problem is of great importance: since in a production campaign many approaches of a product are driven, the probability increases that one or more of these approaches does not have the required quality or have, considerably.

Task and solution

It was the object to develop a process with which it is possible to ensure a consistent, high product quality over a variety of approaches in the production of binders for plastisols. The binders obtainable from this process should allow the formulation of plastisols which should have improved storage stability and, when gelled, improved mechanical properties, namely adhesion, tensile strength and / or elongation at break.

These and other objects which are not explicitly mentioned, but which are readily derivable or deducible from the contexts discussed hereinbelow, are solved by a method having all the features of claim 1. Advantageous modifications of the method according to the invention are described in subclaims 2 to 7 under protection.

With regard to the binder obtainable from the process according to the invention, claims 8 to 13 describe a solution to the underlying problem. Plastisols prepared from the binders prepared by the process of the invention are protected in claims 14 to 18, preferred conditions for their preparation in claim 19 and their use in claims 27-32.

In claims 20 to 26 are claimed plasticized plastisols, with which the solution of the problem underlying the invention is possible.

A surface formulated with a plastisol formulated on the basis of a binder produced according to the invention is protected in claim 33.

An essential element of the method, which enables the solution of the problem is a procedure in which a small amount of a dispersion A was used as the basis for all dispersions B. As a result, all binders produced in a very long period of time are based on a uniform standard.

It has surprisingly been found that the binders prepared by the process according to the invention make it possible to formulate plastisols which are superior to those formulated from conventionally prepared binders. This applies both to properties before gelation (namely storage stability) and properties of the gelled plastisol film (in particular the mechanical properties).

solution

The first step of the process according to the invention is the preparation of a polymer dispersion A. The preparation of this dispersion is in principle subject to no restrictions; suitable for preparation are the usual - known in the art - process for the preparation of primary dispersions (eg, emulsion polymerization, miniemulsion polymerization and Mikroemulsionspolymehsation) and secondary dispersions (in which prefabricated Polymers are dispersed in a second process step). The emulsion polymerization is preferred.

According to the invention, the polymer dispersion A is intended to form the basis for as many as possible production approaches of the binder produced therewith. The proportion by weight of this polymer in the finished binder should therefore be as small as possible. This is achieved when the particles of the polymer dispersion A have a mean particle size (volume average) of not more than 200 nm. Preference is given to mean particle sizes of less than 150 nm, more preferably particle sizes of less than 125 nm. In a particularly advantageous embodiment of the invention, the particles of the polymer dispersion A have a mean size of 80 to 120 nm.

For further embodiment of the method according to the invention, the dispersion A is then - but usually not necessarily together with additional water - placed in a reactor. It may also be useful or necessary to add further additives or auxiliaries (such as, for example, emulsifiers, initiators, electrolytes or chelating agents).

In this reactor, a monomer bi or a mixture of monomers bi is then dosed (a single monomer can in this case as a special case of a

Monomermischung be considered with only one component). This monomer or monomer mixture can be used as such, or together with water,

Emulsifiers and / or other admixtures are dosed.

In typical embodiments of the invention

a homogeneous mixture of the monomer or the monomer mixture with one or more emulsifiers or a homogeneous mixture of the monomer or the monomer mixture with a

Initiator and optionally a coinitiator or an emulsion of the monomer or the monomer mixture in water, optionally with the addition of one or more emulsifiers, metered.

The metering rate (ie how many ml_ per minute are metered to the reactor) can be constant over the metering time or else - if necessary stepwise - vary. Typically, the dosage rate at the beginning of the dosage is lower than the end of the dosage. Monomers which may be used include, for example: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methacrylic acid, acrylic acid, methacrylamide, acrylamide, styrene, butadiene, vinyl acetate, 1-vinylimidazoles, ethylene glycol dimethacrylate, allyl methacrylate.

Monomers whose solubility in water is very poor have proved to be less advantageous for carrying out the invention. As a general rule, it can be assumed that monomers which have a solubility of less than 0.01% by weight at 20 ° C. in water are poorly suitable.

As comonomers in minor amounts (e.g., less than 5% by weight of the

Monomer mixture) poorly water-soluble monomers are usable in some cases.

In a particular embodiment of the invention, monomer mixture bi contains the same monomers in the same proportions by weight as contained in the polymers forming the particles of dispersion A.

In the case that the particles of the dispersion A consist of homopolymers, accordingly and according to this particular embodiment, the monomer bi is the same, which are also contained in the polymers of the particles of dispersion A.

It has been found that the amount of monomers which is metered in this first step, according to the invention must be such that the average particle size of the particles after addition of the monomer or the monomer mixture by at least 50 nm must be greater than that of the particles Dispersion A. The amount of monomers required for this can be estimated with sufficient accuracy by geometrical considerations by taking the volume of particles of dispersion A in relation to the volume of particles after dosing the monomer bi or the monomer mixture bi.

If the amount of monomer needed to reach the particle size increase is greater than expected after the volume increase, then new particles will have formed, which corresponds to a less preferred embodiment of the invention. (In order to avoid this less preferred course, a reduction in the amount of emulsifier, a reduction in the metering rate and / or a reduction in the amount of initiator will generally be able to contribute.)

Optionally, in a further step or in several further

Steps each further monomers b _2, b _3, b _4, ... or monomer b _2, b _3, b _4, ... are added.

For the selection of monomers, the possible addition of water, emulsifier and / or other admixtures, the form of the addition (eg as a homogeneous mixture or as an emulsion) and the metering rate applies to the monomer bi or the mixture of monomers bi said accordingly ,

In this case, the monomers of the further monomers b ₂ , b ₃ , b ₄ , ... or monomer mixtures b ₂ , b ₃ , b ₄ , ... added in later steps should be different from the monomer bi added in the first step or different from the mixture of monomers bi added in the first step.

According to the invention, the mean particle size of the particles in the dispersion should increase by at least 50 nm at each step.

After the last dosage, the polymer dispersion B is thus obtained, which contains as polymer particles the primary particles of the binder to be prepared for plastisols.

The (meth) acrylates and especially the methacrylates have proven to be particularly advantageous from the large number of monomers which can be obtained by the process described.

In a preferred embodiment of the invention, therefore, each of the monomer mixtures used contains at least 50% by weight of one or more monomers which are selected from the group of (meth) acrylates having a residue of not more than 4 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate or iso-butyl (meth) acrylate. A particularly preferred embodiment corresponds to when each of the monomer mixtures used contains at least 70 wt .-% or at least 90 wt .-% of one or more monomers which are selected from the group of (meth) acrylates having a radical of not more than 4 carbon atoms.

If each of the monomer mixtures used contains at least 95% by weight of one or more monomers which are selected from the group of (meth) acrylates having a residue of not more than 4 carbon atoms, this corresponds to a further particularly preferred embodiment of the invention.

By using different monomers and / or monomer mixtures to build up the particles, it is possible to have plastisol properties (such as the

Gelling behavior and storage stability) to adapt to the requirements of the application. In addition to the composition of the individual monomer additions, the total monomer composition of the particles is also important for the properties of the plastisol and the gelled plastisol film.

In a particular embodiment of the invention, the binders comprise at least 25% by weight of methyl methacrylate and at least 15% by weight of butyl (meth) acrylates, the latter being n-butyl (meth) acrylate, isobutyl ( meth) acrylate, tert-butyl (meth) acrylate or a mixture of these monomers can act. In a particularly preferred embodiment, the

Binder at least 50 wt .-% of methyl (meth) acrylate and at least 25 wt .-% of butyl (meth) acrylates.

It has been found that such binders are particularly suitable for the production of plastisols with good storage stability, in which the last of the monomer mixtures added contains at least one monomer which is selected from the group methacrylic acid, acrylic acid, amides of methacrylic acid and amides of acrylic acid.

In a typical embodiment of the invention, between 0.2% and 15% by weight of said monomers are used in the last added monomer mixture. Levels of from 0.4% to 10% by weight are preferred; Contents of 0.6 wt .-% to 5 wt .-% are particularly preferred. The binders obtainable from the process described are also part of this invention.

The primary particles of the binder are inventively larger than the particles of the dispersion A. In a preferred embodiment, they are also greater than 400 nm. Particular preference is given to primary particle sizes of more than 500 nm or more than 600 nm. In a particularly advantageous embodiment of the invention have Particle of the polymer dispersion B has an average size of more than 800 nm.

In order to obtain the binder according to the production method of the invention, the dispersion B is converted by spray drying into a powder, which is then optionally ground.

In a typical embodiment of the invention, a spray tower is used for spray drying, in which the dispersion B is sprayed from above in atomized form. The atomization can be done for example by nozzles or by a rotating perforated disc. The spray tower is - usually in

Direct current from top to bottom - flows through with hot gas. At the lower part of the tower, the dried powder can be removed.

In various ways known to the person skilled in the art, influence can be exerted on the properties of the powder obtained. In addition to the choice of sputtering technique (i.e., nozzle or spinner disk, for example), dispersion pressure, disk speed, nozzle geometry, temperature of the gas entering the tower, and temperature of the exiting gas are exemplified.

In a particular embodiment of the invention, the atomization is achieved by a nozzle through which a gas is sprayed into the tower at the same time as the dispersion under pressure; the relaxing gas breaks the liquid into drops.

The particles of the obtained powder (secondary particles) consist of an agglomeration or aggregation of many primary particles, which is why the average size of the secondary particles is always greater than that of the primary particles.

If desirable or necessary, the average size of the secondary particles be reduced by grinding. Milling can be carried out by one of the methods known to the person skilled in the art; for example with the help of a drum mill or a pin mill.

It has been found that such binders are particularly suitable for plastisol production in which the secondary particle size is at least 12 times as large as the size of the primary particles. Preferably, the size of the secondary particles is at least 20 times as large as the size of the primary particles. Particularly preferred are secondary particles whose size is at least 30 times as large as the size of the primary particles.

For various properties of a plastisol, the molecular weight of the

Polymer chains of the binder of importance; These properties include the storage stability of plastisol paste and the foaming behavior during gelling. As a suitable measure of the molecular weight, the viscosity number is often used. In a preferred embodiment of the invention, therefore, binders are used whose viscosity number (according to DIN EN ISO 1628-1 and at a weight of 0.125 g per 100 ml_ chloroform) is greater than 150 ml / g and less than 800 ml / g. Particularly preferred are binders with viscosity numbers between 180 ml / g and 500 ml / g or between 220 ml / g and 400 ml / g. It corresponds to a further particularly preferred embodiment of the invention, if the viscosity number of the binder (according to DIN EN ISO 1628-1 and at a weight of 0.125 g per 100 ml_ chloroform) is greater than 240 ml / g and less than 320 ml / g.

Furthermore, a plastisol is claimed which can be produced from one of the described binders by adding at least one plasticizer. In general, plastisols in addition to this binder and this plasticizer contain other components such. Fillers, rheology aids, stabilizers, adhesion promoters, pigments and / or blowing agents, and optionally further binders and / or further plasticizers.

In a particular embodiment of the invention, the plasticizer used or, if more than one plasticizer is used, at least one of the plasticizers used has a vapor pressure of 20 ° C. not more than 20 Pa. If several plasticizers or a plasticizer mixture are used, the vapor pressure of the mixture in the composition used at 20 ° C. is preferably not greater than 20 Pa.

In further preferred embodiments of the invention, the corresponding vapor pressures of the plasticizer, one of the plasticizers or the

Plasticizer mixture not greater than 15 Pa, preferably not greater than 12 Pa or, most preferably, not greater than 10 Pa.

One of the decisive factors for processing is the viscosity of a plastisol. Depending on the intended application and the chosen method of application (for example extrusion, dipping, airless spraying) certain maximum viscosities have to be observed.

It therefore corresponds to a particular embodiment of this invention, if the plastisol one hour after its preparation has a maximum viscosity of 25 Pa-s (at 30 ° C), or preferably 20 Pa-s. Particularly preferred are those plastisols whose viscosity has a maximum viscosity of 15 Pa-s (at 30 ° C), or more preferably 12 Pa-s one hour after their preparation.

For the production of plastisols, a variety of possible plasticizers can be used. In addition, mixtures of these plasticizers may also be used. These include:

Esters of phthalic acid, e.g. Diundecyl phthalate, diisodecyl phthalate, diisononyl phthalate, dioctyl phthalate, diethylhexyl phthalate, di-C7-C11 n-alkyl phthalate, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, dimethyl phthalate, diethyl phthalate, benzyloctyl phthalate, butyl benzyl phthalate, dibenzyl phthalate and tricresyl phosphate, dihexyl dicapryl phthalate.

Hydroxycarboxylic acid esters, e.g. Esters of citric acid (for example, tributyl-O-acetyl citrate, triethyl O-acetyl citrate), esters of tartaric acid or esters of lactic acid.

Aliphatic dicarboxylic acid esters, such as, for example, esters of adipic acid (for example dioctyl adipate, diisodecyl adipate), esters of sebacic acid (for example Dibutyl sebacate, dioctyl sebacate, bis (2-ethylhexyl) sebacate) or esters of azelaic acid.

Esters of trimellitic acid, e.g. Tris (2-ethylhexyl) trimellitate. Esters of benzoic acid, e.g. benzyl benzoate

- esters of phosphoric acid, e.g. Tricresyl phosphate, triphenyl phosphate,

Diphenyl cresyl phosphate, diphenyl octyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate.

- Alkylsulfonsäureester of phenol or cresol, dibenzyltoluene, diphenyl ether.

A particular embodiment of the invention is characterized in that more than 50% by weight of the components of the plastisol which are liquid at room temperature are esters of phthalic acid. More preferably more than 70% by weight and more preferably more than 90% by weight of the components of the plastisol which are liquid at room temperature are esters of phthalic acid.

In order to ensure good storage stability of the plastisol paste and to keep the viscosity of this paste as low as possible after production, the

Temperature in the production of the plastisol should be as low as possible. On the other hand, energy is inevitably introduced into the system by mixing the plastisol components, which leads to a temperature increase without cooling. Thus, in consideration of technical requirements, a temperature will be reached which should not be exceeded in the course of plastisol production. It corresponds to a preferred embodiment of this invention, when the temperature in the production of the plastisol temperature of 60 ° C is not exceeded. Preferably, the temperature of the plastisol during its preparation remains below 50 ° C and more preferably below 40 ° C. In a particularly preferred embodiment of the invention, the temperature during the entire duration of the production of the plastisol is not greater than 35 ° C.

Furthermore, the films are claimed, which can be obtained by gelling the said plastisols.

The gelation, sometimes also referred to as 'thermal curing', is usually carried out in a heating oven (eg convection oven) at usual residence times. depending on the temperature - in the range of 10 to 30 minutes. In this case, temperatures between 100 ° C and 200 ° C, preferably between 120 ° C and 160 ° C are often used.

In many applications, the mechanical properties of such a plastisol film is of particular importance, which is also reflected in the task underlying this invention.

If the tensile strength of such a plastisol film, measured according to or according to DIN EN ISO 527-1, is not less than 1 MPa, this corresponds to a particular embodiment of this invention. Further preferred are films whose tensile strength is at least 1, 2 MPa or 1, 5 MPa. Particularly preferred are films having a tensile strength of at least 1.8 MPa or 2.2 MPa.

Another important mechanical property of the plastisol film is the elongation at break, which according to a particular embodiment of the invention - also measured according to or according to DIN EN ISO 527-1 - at least

Should be 180%. Preferably, the elongation at break of the film is not less than 220% or 260%. Films with an elongation at break of at least 300% are particularly preferred.

In general, a good adhesion of the plastisol film is required on the substrate on which it is to be applied. In the automotive industry, this is often a cataphoretically coated steel sheet (The production of such materials has long been known and described many times - see, for example, DE 2751498, DE 2753861, DE 2732736, DE 2733188, DE 2833786), but also other substrates such as untreated steel sheet, Aluminum or plastics are possible.

To assess the adhesion of a plastisol film to the corresponding substrate, it is expedient to proceed according to the wedge film removal method.

For this purpose, the plastiol paste (in the formulation to be used) is applied in a wedge shape to a surface corresponding to the application by means of a doctor blade in such a way that a film thickness of 0 to 3 mm is obtained. The gelled plastisol film (wedge) is transported parallel to the layer thickness gradient a sharp blade at 1 cm intervals cut to the ground. The resulting 1 cm wide plastisol strips are - starting at the thin end - subtracted from the ground.

As a measure of the adhesion, the thickness of the film at the location of the film break is used, where a small film thickness corresponds to a good adhesion. The film thickness at the break-off point is determined with a layer thickness gauge.

According to a particular embodiment of the invention, the plastisol film on untreated, cleaned steel sheet has an adhesion of more than 30 [deg.] .Mu.m according to the wedge-film removal method. The adhesion is preferably more than 50 μm or more than 75 μm. Adhesions of more than 100 μm are particularly preferred.

Also claimed is the use of said plastisols for coating surfaces.

The surfaces may be of different nature, belong to different materials and may be treated; as examples of its surfaces of plastics, wood, chip and wood fiber materials, ceramics, cardboard and / or metals called.

According to a particular embodiment of the invention, the surface to be coated is that of a metal sheet. In a further preferred embodiment, the surface of a metal sheet coated with an electrophoresing paint is coated; these include e.g. also the widely used in the automotive industry KTL sheets.

A corresponding coated metallic surface is also claimed. In this case, the surface to be coated may be e.g. an untreated - possibly oiled - sheet, a cleaned sheet or a KTL-coated sheet metal act.

The plastisols produced according to the invention are particularly suitable for use as underbody protection and for seam sealing, above all in the automotive industry and wagon construction.

Furthermore, they can be used with advantage anywhere where the vibration of a surface is to be damped. Examples of such applications in private households include the cladding of household appliances, such as washing machines, refrigerators, food processors and air conditioning. Furthermore, the disguise of personal computers. Examples of construction and construction materials are pipes, floors and wall coverings.

Particularly preferred is the coating of body parts in the automotive industry. If the coatings are used on the outside in the underbody and wheel housing area of the motor vehicle, in addition to the damping of the sheet metal vibrations, the impact noise of stones, sand and water is also reduced.

methods

viscosity

The viscosity number or reduced viscosity [η] of a solution can be used as a measure of the average molecular weight.

A rough estimate of the molecular weight is taken therefrom according to the Mark-Houwink relationship using the Mark Houwink constants a = 0.83 and K _v = 0.0034 mL / g (for polymethyl methacrylate homopolymers at 25 ° C. in chloroform) "Polymer Handbook: Fourth Edition", J. Brandrup, EH Immergut, EA Grulke) possible:

[η] = K _v ^■ M ^a; Mark-Houwink relationship

Accordingly, for average molecular weights of about 400,000 g / mol, a viscosity number of about 150 ml / g is expected; for average molecular weights of about 1,000,000 g / mol, a viscosity number of about 325 ml / g is to be expected.

Unless otherwise stated, the viscosity number values given in this document have been determined in accordance with DIN EN ISO 1628-1 and at a weight of 0.125 g per 100 ml of chloroform.

particle size

For measuring the particle size, the person skilled in a number of methods are known. A common - also for the measurement many samples like those at the

Production control is practicable - method is that of laser diffraction. A detailed description of this method is contained in DIN ISO 13320-1. To carry out one can for example use a 'Coulter LS 13 320' from the manufacturer Beckmann-Coulter. vapor pressure

The determination of the vapor pressure can be carried out according to the method described in DIN EN 13016-1 (Edition: 2006-01).

Tensile strength / elongation at break

The determination of the vapor pressure can be carried out according to the method described in DIN EN ISO 527-1.

Adhesion according to the wedge film removal method

The plastiol paste (in the formulation to be used) is applied in a wedge shape to a surface to be examined with a doctor blade in such a way that a film thickness of 0 to 3 mm is obtained.

The gelled plastisol film (wedge) is cut parallel to the layer thickness gradient with a sharp blade at 1 cm intervals down to the substrate. The resulting 1 cm wide plastisol strips are - starting at the thin end - subtracted from the ground.

As a measure of the adhesion, the thickness of the film at the location of the film break is used, where a small film thickness corresponds to a good adhesion.

The film thickness at the break-off point is determined with a layer thickness gauge.

Solids content

The solids content of the dispersions can be determined experimentally by weighing a defined amount of dispersion on a flat aluminum pan. This dish is dried in a vacuum oven at 50 ° C to constant weight.

The solids content is calculated by {weighting of the dried polymer} divided by {dispersion weight}. Preparation Examples

Comparative Example C1 (According to the Prior Art)

A 500 ml reactor is equipped with a thermometer, a port for inert gas (nitrogen), a stirrer, a dropping funnel and a reflux condenser.

In this reactor, 150 g of water are introduced and tempered by means of a water bath to 80 ° C.

The reactor is superimposed with a slight stream of nitrogen until the end of dispersion production. By heating and cooling, the temperature is maintained at 80 ° C throughout the reaction time. The contents of the reactor are stirred with a stirrer at 200 revolutions per minute.

50 mg of potassium peroxodisulfate (initiator) are added to the reactor. Immediately afterwards, a mixture of 0.08 g of diisooctylsulfosuccinate (emulsifier) with 17.32 g of methyl methacrylate 22.68 g of isobutyl methacrylate is metered into the reactor at a rate of 20 g / hour. After the end of the dosing, stirring is continued for one hour until the intermediate reaction time has ended. Subsequently, a mixture of 0.06 g of diisooctylsulfosuccinate (emulsifier) with 30.83 g of methyl methacrylate and 29.17 g of n-butyl methacrylate is metered into the reactor at a rate of 20 g / hour. After the end of the metering, stirring is continued for one hour until the post-reaction time has ended. After cooling, the dispersion is filtered through a gauze (mesh size 250 microns).

In a drying tower (Niro, atomizer type) with centrifugal atomizer, the polymer dispersion is converted into a powder. The tower outlet temperature is 80 ° C; the speed of rotation of the atomizer disk is 20000 min ^-1 .

Example E1 (according to the invention)

A 500 ml reactor is equipped with a thermometer, a port for inert gas (nitrogen), a stirrer, a dropping funnel and a reflux condenser fitted.

In this reactor, 100 g of deionized water and 1, 00 g

Diisooctylsulfosuccinat (emulsifier) submitted and by means of a water bath

Tempered at 80 ° C. The reactor becomes weak until the end of dispersion production

Nitrogen flow superimposed. The contents of the reactor are mixed with a stirrer

200 revolutions per minute stirred.

In a separate container (emulsion master) 48.98 g of methyl methacrylate,

64.14 g of isobutyl methacrylate, 1.30 g Diisooctylsulfosuccinat and weighed 50 g of deionized water. Stirring (10 minutes at 200 revolutions per minute) produces a homogeneous emulsion.

50 mg of potassium peroxodisulfate are dissolved in an Erlenmeyer flask and 1 ml of water in another 50 mg of Nathumdisulfit.

30 g of the emulsion from the emulsion master are transferred to the reactor. Then the polymerization by addition of the attached Nathumperoxodisulfat- and

Nathium disulfite solutions started.

After the temperature in the reactor has risen by 2 ° C, the remaining

Emulsion at a rate of 50 g / hour metered into the reactor. Optionally, cooling with the water bath prevents the temperature in the reactor from rising above 86 ° C.

After the end of the dosage is stirred for an hour until the

Post-reaction time is completed.

After cooling, the dispersion ('Dispersion A') is passed through a gauze

(Mesh size 250 microns) filtered.

The solids content of this dispersion A (determined experimentally) is 44.0% by weight; the average particle size is 104 nm.

According to this example, the dispersion A can be used as a raw material for about 500 dispersion batches B in the binder production.

For the preparation of the dispersion B is then proceeded largely analogously to Comparative Example V1. The only change - after the water introduced has reached the temperature of 80 ° C and before the initiator potassium peroxodisulfate is added - added 0.5 ml_ of the dispersion A in the reactor. Discussion of examples

Both the primary particles of comparative example V1 and those of dispersion B in inventive example E1 have a composition of 52:48 (mol%) of methyl methacrylate to isobutyl methacrylate in the interior. The outer region of the particles obtained in the second monomer metering consists in both cases of methyl methacrylate and n-butyl methacrylate in a ratio of 60:40 (mol%). The particles of Dispersion A in Example E1 according to the invention have the monomer composition 52:48 (mol%, methyl methacrylate to isobutyl methacrylate) (and thus the same as the first dosage in the preparation of Dispersion B in Example E1).

The dispersion in Comparative Example C1 was prepared 6 times, with average particle sizes between 673 nm and 861 nm were obtained. The mean value from the experiments was 784 nm.

The dispersion B produced repeatedly in Example E1 according to the invention with the aid of the same dispersion A exhibited a significantly lower scattering of the mean particle sizes: for an average of all 6 experiments of 806 nm, the lowest particle size measured was 792 nm; the largest particle size measured was 817 nm.

While the slow metering in the comparative example V1 (especially at the beginning of the first metering) is decisive, in the example according to the invention E1 can be metered from the outset at a higher rate: for example, a doubling of the metering rates has no effect in the example E1, while the achievable particle size is significantly smaller in the comparative example V1. The particle size achieved is correspondingly sensitive to unintended fluctuations in the dosing rate.

Claims

claims

1. A process for the preparation of a binder for plastisols, characterized in that - first a polymer dispersion A is prepared whose particles are not larger than 200 nm

- Then a portion of the dispersion A is optionally presented together with additional water and / or additives or excipients in a reactor and

- A monomer or a monomer mixture, wherein the or each of the monomers has a water solubility of more than 0.01 wt .-% at 20 ° C, optionally dosed together with water, emulsifier or other admixtures to this reactor and polymehsiert there so that the average size of the particles increases by at least 50 nm, and then - optionally one or more further monomers or

Monomer mixtures other than the first monomer or monomer mixture and wherein also or each of the monomers has a water solubility of more than 0.01% by weight at 20 ° C, optionally together with water, emulsifier or others

Admixtures are dosed to this reactor and there polymehsiert so that the average size of the particles increases by at least 50 nm, and

- Then, by spray-drying the resulting dispersion B, a powder is obtained, which is so or optionally milled in whole or in part, the binder.

2. A process for producing a binder for plastisols according to claim 1, characterized in that the monomer composition of the particles in dispersion A is the same as that of the first added monomer mixture.

3. A process for the preparation of a binder for plastisols according to claim 1, characterized in that each of the monomer mixtures used contains at least 50 wt .-% of one or more monomers which are selected from the group of (meth) acrylates having a residue of not more as 4 carbon atoms.

4. A process for the preparation of a binder for plastisols according to claim 1, characterized in that each of the monomer mixtures used contains at least 90 wt .-% of one or more monomers which are selected from the group of (meth) acrylates with a balance of not more as 4 carbon atoms.

5. A process for the preparation of a binder for plastisols according to claim 1, characterized in that each of the monomer mixtures used contains at least 90 wt .-% of one or more monomers which are selected from the group of methacrylates having a radical of not more than 4 carbon atoms ,

6. A process for the preparation of a binder for plastisols according to claim 1, characterized in that the last of the added monomer mixtures contains at least one monomer selected from the group of methacrylic acid, acrylic acid, amides of methacrylic acid and amides of acrylic acid.

7. A process for the preparation of a binder for plastisols according to claim 1, characterized in that the last of the monomer mixtures added contains 0.2 wt .-% to 15 wt .-% of monomers selected from the group of methacrylic acid, acrylic acid, amides of methacrylic acid and Amides of acrylic acid.

8. Binder preparable according to one of claims 1 to 7.

9. A binder according to claim 8, characterized in that

- The primary particles have a mean diameter of more than 400 nm and

- The average diameter of the secondary particles is at least twelve times as large as the average diameter of the primary particles.

10. A binder according to claim 8, characterized in that

- The primary particles have a mean diameter of more than 600 nm and

- The average diameter of the secondary particles is at least 20 times as large as the average diameter of the primary particles.

11. A binder according to claim 8, characterized in that in the overall composition of the polymers not less than 25 wt .-% of methyl methacrylate and not less than 15 wt .-% of butyl methacrylate (s) are included.

12. A binder according to claim 8, characterized in that contained in the overall composition of the polymers not less than 50 wt .-% of methyl methacrylate and not less than 25 wt .-% of butyl methacrylate (s).

13. A binder according to claim 8, characterized in that the viscosity number according to DIN EN ISO 1628-1 a solution of 0.125 g

Binder per 100 ml_ chloroform is greater than 150 ml / g and less than 800 ml / g.

14. Plastisol, producible with a binder according to one of claims 8 to 13.

15. plastisol according to claim 14, characterized

- That it contains at least one plasticizer which has a vapor pressure of not more than 20 Pa at 20 ° C, and

- That it has a viscosity of less than 25 Pa-s measured at 30 ° C 60 minutes after the preparation.

16. plastisol according to claim 14, characterized

that it contains at least one plasticizer which has a vapor pressure of not more than 12 Pa at 20 ° C, and

- That it has a viscosity of less than 15 Pa-s measured at 30 ° C 60 minutes after the preparation.

17. Plastisol according to claim 14, characterized in that more than 50% by weight of the components of the plastisol which are liquid at room temperature are esters of phthalic acid.

18. plastisol according to claim 14, characterized in that more than 90% by weight of the liquid at room temperature components of the plastisol esters of

Phthalic acid are.

19. Preparation of a plastisol according to any one of claims 14 to 18, characterized in that the paste is not warmer than 60 ° C in the production.

20. A gelled plastisol film obtainable from a plastisol according to any one of claims 14 to 18.

21. A gelled plastisol film according to claim 20, characterized in that the gelled film has a tensile strength of not less than 1 MPa.

22 gelled plastisol film according to claim 20, characterized in that the gelled film has a tensile strength of not less than 1, 8 MPa.

23 gelled plastisol film according to claim 20, characterized in that the gelled film has an elongation at break of not less than 180%.

24. A gelled plastisol film according to claim 20, characterized in that the gelled film has an elongation at break of not less than 260%.

25. gelled plastisol film according to claim 20, characterized in that the gelled film has an adhesion of more than 30 microns after

Keilfilmabzugsmethode has.

26 gelled plastisol film according to claim 20, characterized in that the gelled film has an adhesion of more than 75 microns after the Keilfilmabzugsmethode.

27. Use of a plastisol according to any one of claims 14 to 18 for coating surfaces.

28. Use of a plastisol according to any one of claims 14 to 18 for coating sheets.

29. Use of a plastisol according to any one of claims 14 to 18 for coating electrophoretically dip-coated sheets.

30. Use of a plastisol according to any one of claims 14 to 18 for underbody protection.

31. Use of a plastisol according to any one of claims 14 to 18 as seam cover.

32. Use of a plastisol according to one of claims 14 to 18 for damping sheet metal vibrations.

33. Coated metallic surface, characterized in that the coating is carried out with a plastisol according to one of claims 14 to 18, optionally after previous electrodeposition.