FR2558476A1 - PREPARATIONS OF ENHANCED ADHESION POLYMERS, SUITABLE FOR COATING, AND THEIR PRODUCTION - Google Patents

Abstract

PREPARATIONS OF POLYMERS FOR COATING SUBSTRATES, CONTAINING OWN KNOWN P POLYMERS SUITABLE FOR COATING, AND 5 TO 50 BY WEIGHT OF HP POLYMERIZATION PRODUCTS PROMOTING ADHESION, WHICH CONSIST OF: A. AT LEAST A MONOMER OF FORMULA I (CF DRAWING IN BOPI) WHERE R IS H OR A PHENYL AND X IS: 1-CYQZ, Y IS O OR AN AMINE, Q A GAP GROUP AND Z A GROUP: -CH-CH; -O-CH-O-CH; - (OCHCH) OR ;-( OCH-CH) -NRR; - (OCHCH) -CN; -SOH; -OPOHR; -OCQ-COOH, OR R AND Q HAVE THE SAME MEANINGS AS R AND Q, M IS 0, 1 OR 2, AND R AND R ARE H, AN ALKYL OR A HETEROCYCLIC CORE, OU2- (CH) -R, N BEING 0, 1 OR 2 AND

Description

The invention relates to polymer preparations, which are

  advantageously for powder coating and plastic coating.

  tisol, preparations which have improved adhesion to the supports and which contain, in addition to the known polymers P, suitable for coating, HP copolymers which act as adhesion promoters, as well as a process for their production.

  The powder coating and the plastisol coating represent

  feel modern techniques for the application of thin layers on surfaces, in particular of metal or material

  synthetic material, without the use of large quantities of

  solvents. For this reason, these methods can be considered extremely low polluting. Another advantage is the

  fact that their application can be largely automated.

  As the name suggests, as a general rule

  thermosetting polymer powders (for enamel powders).

  Suitable for example enamel powders which are manufactured based on epoxy resins, polyethylenes, polyesters, CPV,

  of polyamide, cellulose acetate butyrate, chlorinated polyethers

  res, ethylene-vinyl acetate copolymers, polymetallic

  methyl crylate, alkyd and amino resins and hydrocar-

  fluorinated burs (see Ullmanns Encyklopadie der Chemie Chemie, 4th edition, vol.15, pages 660-664, 693, Verlag Chemie). Different methods of application are used in this case, for example the rotary or flocking process, the centrifugal casting in the fluidized bed plastic coating bath, the flame spraying and in particular the electrostatic color powder coating. In general, the methods of application include sintering, that is, particle fusion.

  of synthetic material under the effect of heat. In case of use

  thermosetting resins, this operation is

followed by a cooking cycle.

  In some cases, the adhesion of the polymers P to the supports

  intended for coating, in particular to metal surfaces

  to a sufficient extent to meet the requirements of practice. Adhesion agents used in general are multifunctional, low molecular weight or oligomeric liquids, for example polyaminoamides and / or polyamines. But when using the liquid adhesion agents, there are new problems, due for example to the relatively high vapor pressure of the adhesion agents, so that we can have concerns of ecological and industrial hygiene. The enamel powders may optionally contain plasticizers. Plastisols represent

  a special form, frequently used.

  plastisols have also found a wide range of

  in the coating of substrates (metals, textiles, wallpapers, cable insulation, etc.). Plastisols can be considered as two-phase systems with sizes

  particles in the border region between the upper colloids

  (particle size: 104 to 10 6 cm) and the range

  detectable under the light microscope (size of

  10-3 to 10-5 cm) (see K. Weinmann, "Deutsche Farben-

  Zeitschrift, 1 (3) pp. 93-106, 1965) In these conditions, the synthetic materials or resins constitute a dispersed "internal" phase, the continuous "external" phase is formed by plasticizers. are first pasty and easy to handle, are transformed, following the cooking (= absorption of the plasticizer by the polymer which is

  originally in the dispersed state), in the synthetic

  desired test, containing a plasticizer, in which the poly-

  mother is now also part of the continuous phase.

  In addition to the disadvantages already mentioned

  liquidity, it is necessary to consider in addition, in the formulas

  plastisols, the adverse influence on the rheology of the pastes by the liquid adhesion

  example the interaction of adhesion agents, often cationic

  with anionic thixotropic adjuvants.

  There was therefore the problem of improving the adhesion of known polymeric coating products to substrates, in particular metal substrates, as far as possible without adversely affecting the practicability of polymers and without disadvantages for the other characteristics of polymeric coating products. It has been discovered that polymer preparations achieve this goal to a large extent when they contain, besides the known P polymers, suitable for coating, at 50% by weight (based on P polymers) of HP polymers. adhesion promoters which consist of: A) from 0 to 100 - by weight, preferably from 0.5 to 50% by weight, of at least one monomer of IR formula

CH2 = C - X (I)

  wherein R 1 is hydrogen, an alkyl radical of 1 to 6 carbon atoms in a straight or branched chain or a phenyl radical and X has the following meanings C (1) - c -YQ-z Y being for an oxygen atom or for -NR2 (R2 being a

  hydrogen atom or an alkyl radical with 1 to 6 carbon atoms

  n), Q for a hydrocarbon chain with 1 to 10 carbon atoms, optionally branched or for a cyclic radical with 5 to 10 carbon atoms and Z for a group -CH -CH 2; -O-CH2-O-CH3; - (OCH2CH2) m-OR'2; (OCH2-CH2) m-R3R4; - (OCH2CH2) m-CN;

-S3H; -OP3HR'2; -OC-Q '- COOH

  In which R'2 and Q 'have the same meanings as R2 and

  that Q, m is put for 1, 2 or 3 and in which R3 and R4, inde-

  from each other, are hydrogen or an optionally branched alkyl radical, or R3 and R4 form, 3C with nitrogen, a 5- or 6-membered heterocyclic ring which may contain nitrogen or oxygen, or (2) - (CH2) n-R5

  n being equal to C, 1 or 2 and R5 being set for a group of

0 O

  ! mule - C - Y '- Bs; - - Bs or -Bs, wherein Y' has the same meaning that Y and Bs represents a heterocyclic group containing one or more rings and having at least one nitrogen atom in the ring, or

3) -COOR6

  wherein R6 is hydrogen or an alkaline cation

  or ammonium, and B) for 0 to 99.5% by weight, preferably 50 to 99.5% by weight.

weight of monomers of formula II-

R

H2 C - R8 (II)

  wherein R7 is hydrogen or methyl

  and R8 for a -COOR9 radical, where R9 is an alkyl radical optionally

  cyclic to 1 - 8 carbon atoms, or R8 is put

  for a phenyl radical optionally substituted with radicals

  alkyl groups with 1 to 4 carbon atoms, and C) for 0 to 10% by weight of monomers of formula III

H00C - A - COOH

  in which A represents a radical with 2 to 12 carbon atoms

  containing at least one double bond in position d with respect to the carboxyl group and / or the internal anhydride or cyclic imide derived from the dicarboxylic acids of formula III, with the proviso that the sum of the monomers A) plus B) is always raises to at least 90% and up to 100% by weight of the adhesion-promoting HP polymer and that the vitrification temperature of the adhesion-promoting HP polymer is

in the range of 40 to 150 C.

  With regard to the polymers P, these are solid bodies

  (at room temperature), as a rule of solids

  in the form of particles or grains. In general, the average grain size is in the range of 0.1 to 500 μm (determination according to B. Scarlett, Filtration and

Separation, May / June 1965, p. 216).

  The polymers P are generally part of the group of epoxy resins, polyethylenes, polyesters, CPV,

  polyamide, cellulose acetate butyrate, chlorinated polyethers

  res, ethylene-vinyl acetate copolymers, polymetha-

  methyl crylate, alkyd and amino resins and hydro-

  fluorinated carbides. Polymer-based enamel powders are suitable

  particularly well in the sense of the present invention-

  (see the discussion of the state of the art which precedes). The

  The polymer preparations according to the invention are particularly

  suitable for powder coating applications

  (see Ullmanns Encyklopadie, 4th edition, vol.15, op cit).

  But they can also be used as plasticizers

  soils in the form of the preparations usually used for this purpose [cf. K. Weinmann, Deutsche Farben-Zeitschrift 12, (3), pp.

  93-106 (1965) _A. The preparation of polymeric plastisols

  For example, acrylate resins P is described in DE patents.

  24, 54, 235, 29, 732, 43, 542 and 27, 22, 752.

  For the case where the combination according to the invention of poly-

  P-solids with adhesion-promoting HP solids are used in the form of a plastisol, further care should be taken to ensure that the P polymers, such as

  HP polymerization products are not spontaneously dissolved

  in the plasticizers used. A particular way

  appropriately to pocket premature interaction between

  HP polymerization product and another component of the prepa-

  The use of polymers, for example a thixotropic adjuvant, consists of giving a core-shell structure to the HP polymerization product. For this purpose, it is advantageous to use as a shell material a polymer incompatible with the plasticizer, having such a high vitrification temperature.

  as possible, for example a polymerized methyl methacrylate.

  For example, the above-mentioned patents contain combinations of

  plasticizer / polymer sounds that are suitable.

  As X-adhesion promoting HP polymerization products having the meaning (1) in the monomers of the formula I are preferred those in which glycidyl acrylate and methacrylate are used as monomers of the formula I alkyl aminoalkylacrylates and methacrylates,

  amides and methacrylamides of alkylaminoalkylacrylic acid

  alkoxyalkyl acrylates and methacrylates and the

  corresponding amides, acrylates and methacrylates of Ca-cyano

  alkaloids, alkyl esters or amides, sulfonated or phos-

  phonylates at the end of the chain, acrylic acid and / or methacrylate

  as well as alkyl acrylates and methacrylates

  esterified once at the end of the chain with dicarboxylic acids

  preferably from 5 to 100% by weight, and in particular from 10 to 50% by weight, relative to the product of

HP polymerization.

  For example, acrylate or methacrylate of

  2-dimethylamino- and 2-diethylaminoethyl, acrylate or metha-

  2-dimethylamino- and 2-diethylaminopropyl crylate, 2-tert-butylaminoethyl acrylate or methacrylate, as well as

  3-dialkylamino-2,2-dimethylpropyl acrylates and methacrylates

  le-1, in particular the compounds 3-dimethylamino and 3-diethyl-

  amino, and the amides (Y = NR2, R2 being hydrogen, methyl or ethyl) of the compounds mentioned above, for example

  N, N-dimethylaminopropylacrylamide and N, N-dimethylamino-

  propylmethacrylamide. In addition, morpholinoethyl (meth) acrylate and the corresponding amides deserve interest. Furthermore, mention may be made, as polymerizable monomers in which X has the

  significance (2), N- or C-vinyl compounds or N-. or C-

  allyl imidazole, imidazolidine, imidazoline,

  benzimidazole, pyrazole, pyrrole, triazole, oxa-

  zole, pyridine, diazine, quinoline, oxy-

  quinoline. N-vinilimidazole is particularly interesting.

  The proportion of the monomers of formula I in which X has the meaning (2), relative to the polymerization product HP, is generally between 0.5 and 10% by weight,

  in particular in the range of 1.5 to 5% by weight.

  If desired, the HP polymerization products may be further composed of monomers of formula II. Mention may be made of methacrylates and acrylates of C1 to C8 alcohols, in particular the methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl and tertiary butyl esters,

  2-ethylhexyl, cyclohexyl, and especially methacrylate

  methylate. In addition, mention may be made of styrene and its derivatives, for example methyl-styrene and p-methylstyrene. the

  proportion of the monomers of formula II in the product of poly-

  HP is about 0 to 99.5% by weight, preferably

  from 50 to 99.5% by weight. Finally, polymer products

  HP may also be constituted, where appropriate, dicarboxylic acids of formula III or their anhydrides or imides, as comonomers. We will mention maleic acid

  and its anhydride or imide, fumaric acid, itaconic acid.

  HP adhesion-promoting polymerization products generally have a molecular weight M in the range of 5,000 to 500,000, preferably 10,000 to 200,000.

after Houben-Weyl, op. cit9).

  The choice of the monomers is expediently made in such a way that the vitrification temperature Tg resulting from the adhesion-promoting HP polymerization product is in the range from 40 to 150.degree.

  IL polymerization product, a mixture of polymers, the

  the temperature of at least one of the constituents of the mixture must be in the range of 40 to 150 C), preferably in the range of

from 60 to 110 C.

  The vitrification temperature of copolymer products

  can be calculated for example from the values given in

  Vaccines of monomers (see TG Fox, Am Bull Physics Soc., 1, 123 (1956) and Vieweg-Esser, "Kunststoff-Handbuch", IX, C. Hanser-Verlag, Munich, 1975, pp. 333-339, where the method of

measurement is also indicated).

  Preparation of HP polymerization products favoring

  adhesion can be effected, in a manner known per se, by poly-

  radicalization of the monomers, for example by polymerisation

  3C in emulsion or by mass polymerization (see Houben

  Weyl, vol. 14/1, Georg-Thieme-Verlag, Stuttgart, 1961). In all

  However, it is necessary that the polymerisation product

  Finally, it is in the form of a solid material in very fine particles (particle size of between 0.01 and 10 μm, preferably between 0.05 and 10 μm). For example, a mass polymerization product must be

crushed very finely.

  The fact that HP polymerization products favoring

  adhesion is in the form of particulates

  This is important because it is only in this way that they mix

  These polymers are suitable for coating, and only in this way do they melt sufficiently quickly. This is why emulsion polymerization and microsuspension polymerization are of particular interest for the preparation of the adhesion-promoting HP polymerization product, since with this process the polymerization product

  is obtained in the form of fine particles.

  Particular preference is given to poly-

  Emulsion merification that has a particle size

from 0.05 to 5 μm.

  recovering the solid matter from the polymer product

  from the dispersions of polymers is carried out by precipitation of these dispersions, for example by addition of salt, extraction of the product precipitated by washing, followed by

  drying. Your recovery of the solid matter from the pre-

  The precipitation from the aqueous polymer dispersion is also possible by coagulation by freezing, followed by drying, or by direct freeze-drying. We will however prefer

  recovering the solid matter from the polymerization product

  spray drying. Spray drying

  In general, this leads to small, slightly aggregated grains having a diameter in the range of 3 to 300 μm, the diameter

  The average particle size is generally from 10 to 50 μm.

  These particles of 10 to 50 μm in size are therefore formed by more or less loose agglomeration of dispersion particles.

from 0.05 to 5 μm in size.

  The emulsion polymerization process is also suitable

  Particularly good for the preparation of poly-

  HP meriting adhesion because it offers the possibility

  It is possible to produce polymer particles of 0.05 to 5 μm in size having a core and shell structure. In this respect, the teachings of DE-A 27 22 752 can be closely followed. This core and shell structure makes it possible, for example, to form a material which comprises, as a core, polymerization products having groups that promote adhesion and, as an envelope, products

2558476,

  of polymerization lacking such adhesion promoting groups.

  This is particularly interesting when there is already reason to fear, in the actual fusion, the interactions of the adhesion promoting groups (eg amines) with other constituents of the formulation. In addition, a core and shell structure offers the possibility of obtaining, in the form of solid powders, particularly soft copolymerization products (for example those which have a vitrification temperature of 30 ° C. and which can absolutely not be obtained by drying. by spraying) by

  coating with a harder polymerization product, for example

  by a polymerization product having a vitrification temperature of more than 40 C. In general, it is possible to

  say that when the polymerization product promotes adhesion

  the structure of an emulsion polymerization product

  with core and casing, at least the envelope of the product of poly-

  merification must have an equal vitrification temperature

or greater than 40 C.

  The emulsion polymerization products can advantageously be prepared according to the flow addition method of the emulsion or monomers, a part of the water and the total amount or fractions of the initiator and

  of the emulsifier being introduced beforehand. With this procedure

  the particle size can be controlled advantageously

  the amount of emulsifier introduced beforehand.

  As emulsifiers, anionic, nonionic and cationic surfactants can be used. In general, the amount of emulsifier used will not exceed 1% by weight - based on the polymerization product. As initiators, it is possible to use, in addition to the usual compounds in emulsion polymerization, for example "per" compounds such as hydrogen peroxide or ammonium peroxydisulfate (APS), redox systems such as bisulfite. -APS-iron, as well as azo initiators. The proportion of initiator is in general between 0.005 and 0.5% by weight relative to the polymerization product (see H. Rauch-Puntigam, T. V. Lker, "Acryl- und Methacrylverbindungen", Springer-Verlag, 1967 , pp.

217-230).

  the polymerization temperature depends, within certain limits, on the initiator. Thus, in the case of using APS, it is advantageous to operate in the range of 60 to 90 C.

  oxidation-reduction systems are used, it can even be

  kill the polymerization at lower temperatures, for example about 30 ° C. Beside the flow addition polymerization, it is also possible to operate according to the process of batchwise polymerization. In this case, the total amount or a fraction of the monomers is introduced beforehand with all the adjuvants and the polymerization is initiated with the aid of redox initiators. In that case,

  the monomer-water ratio must be adapted to the heat of reaction

  which is unobstructed. As a rule, no difficulty is encountered when producing a 50% emulsion by first emulsifying half of the monomers and adjuvants in the total amount of water, then initiating the polymerization at room temperature and when the reaction has occurred, cooling the charge and adding the remaining half of the

monomers with adjuvants.

  Filtration of the dispersions is advantageously carried out by means of stainless steel fine mesh filter cloths.

presenting 100 meshes / cm.

Example 1

  1.1 Preparation of the dispersion 1.5 g of ammonium peroxydisulfate and 0.6 g of C15 paraffin sulfonate (commercial designation: Emulsifier K30, Bayer AG) are dissolved at 80 ° C. in 1200 g of water, in a pot of Witt (6 l) equipped with a reflux condenser, a stirrer and te, crushed in the form of fine powder (<60 / u). 15 parts by weight of a polymerization product according to Example 5.2 for parts by weight of this mixture are incorporated in one embodiment. Except ml: Yln un107: T'l tiOf nT rnitiP. the aforementioned emulsifier, 1.5 g of the aforementioned initiator and 1818 g of water. After the end of the addition, the charge is maintained at 8000 for a further 2 hours, cooled to room temperature and filtered through a fine mesh filter cloth

stainless steel.

  Your dispersion has a solids content of 49.9%.

2558476,

1 1

  Diameter of the latex particles: 192 nm.

  1.2 Dispersion drying The dispersion is sent to a spray drying plant, with a spraying disc which rotates rapidly (20 000 rpm), to compete with air at 130 ° C. The quantitative dispersion / air ratio is adjusted in such a way that the sprayed product leaves the installation at an outlet temperature of 70 C in the form of a dry powder,

  finely divided, white, containing no constituents

trous.

  Main fraction, 15 to 25 μm. Larger particles, 70 -

  / Um; apparent density, 350 g / l. Vitrification temperature

Tg = 95 C.

  1.3 Production of oleparation and coating

  70 parts by weight of CPV (K value, 65;

  25%), parts by weight of TiO 2 (rutile type), parts by weight of DOP (dioctyl phthalate), 1.5 parts by weight of CPV stabilizer, based on tin mercaptide. dibutyl

  parts by weight of polymer powder according to the

  1.2 are mixed homogeneously in a forced-blending mixer and conditioned at 400 ° C. for 24 hours. Then the agglomerates are broken in a stirrer rotating rapidly. the powder thus obtained is electrostatically applied, in a manner known per se, to an iron screed with a layer thickness of approximately 50 μm and then fired at 205 ° C. for 15 minutes. The coating has a specular glossy finish, good continuity and does not come off

  support in case of manual mechanical stress.

  Without addition of the polymer powder according to Example 1.2 above, the coating can be easily detached from the sheet metal.

of iron.

Example 2

2.1 Preparation of the dispersion

  1.8 g of the sodium salt of 4,4-azo-bis- (4-cyanovaleric acid)

  that) and 1.8 g of sodium dodecyl sulphate are dissolved at 80 ° C. in 1460 g of water, in a Witt pot (6 l) equipped with a

2558476.

  reflux condenser, agitator and flow addition vessel. To this solution, we add drop by drop,

  with stirring and within 2 hours, the emulsion 1.

  Emulsion 1 (core material): 840 g of 3-dimethylamino-2,2-dimethylpropyl-1-methacrylate, 360 g of methyl methacrylate, 6 g of 2-ethylhexyl thioglycolate, 8.1 g of sodium dodecyl sulphate. sodium, 2.7 g of 4,4-azo-bis- (4-cyanovaleric) sodium salt,

1094 g of water.

  Then, within 2 hours, we proceed to the addition of

the emulsion 2.

  Emulsion 2 (shell material): 1200 g of methyl methacrylate, 8.1 g of sodium dodecyl sulphate, 2.7 g of 4,4-azo-bis (4-cyanovaleric) sodium salt,

1094 g of water.

  After everything has been added, the load is maintained

  2 hours at 80 ° C., then cooled to about 25 ° C. and filtered at

  through a fine mesh filter cloth of stainless steel.

  The dispersion has a dry matter content of 39.7%.

  2.2 Drying of the dispersion The procedure is as indicated in Example 1, with the difference that the hot air supply is at 14500 C.

  outlet air temperature is 66 0C.

  The result is white, non-glassy pearls; fraction

  main 20 - 30 / um, larger particles 64 - 70 / um.

  Vitrification temperature, Tg: with the two-phase structure, two values of Tg: Tg1 (core material) were found: about 600 ° C; Tg2 (envelope material)

About 10500 C.

  2.3 Production of my preparation of eolemers and coating

  parts by weight of PVC powder (K 70 value,

  particle size <60 / u for 90%), parts by weight of diisononyl phthalate, 8 parts by weight of polymer powder of ex. 2.2

  parts by weight of chalk (particle size less than

above 85 / u for 95%).

  are homogenized in a three-roll mill and

  without compressed air, in a manner known per se. the support to be coated is an iron plate coated with synthetic resin by cataphoresis (primer). After gelation of the material applied for 30 minutes at 130 ° C., a well-adhering coating is obtained which can be used, for example, to protect rocker panels for

motor vehicles.

  Without the use of the polymer powder according to the

  2.2 above, the gelled film can be detached from the support.

Example 3

3.1 Pre] aration of the dispersion

* 3 g of the sodium salt of 4,4-azo-bis- (4-cyanovaleric acid)

  that) and 6 g of sorbitan-polyoxyethylene monooleate are

  at 80 ° C. in 1260 g of water, in a Witt pot (21) equipped with a reflux condenser, a stirrer and a flow addition vessel. To this solution is added with stirring,

  space of 4 hours, a mixture of monomers and emulsifier,

  lable prepared from 600 g of methyl methacrylate, 200 g of 2-dimethylaminoethyl methacrylate and 18 g of the emulsifierprécité. After completion of the flow addition, 1.2 g of the above-mentioned initiator is added and stirred.

  the charge at 80 C for 2 h. After cooling down to

  ambient, filter on a fine mesh filter cloth

stainless steel.

  The dispersion has a solids content of 39.6%.

Particle diameter: 228 nm.

3.2 Drying the dispersion

  The procedure is as indicated in Example 1.

  Powder in fine particles. Vitrification temperature, Tg:

 C about.

  3.3 Production of the reparation of the stars and coating

  parts by weight of PVC powder (K-value 62, gross

  particle size, 50 / u for 95%), parts by weight of TiO 2 (rutile type), 3 parts by weight of benzyloctyl phthalate, parts by weight of polymer powder of Example 3.2,

  2 parts by weight of mercapto-based CPV stabilizer

  Tin-dibutyl tide is homogeneously mixed in a forced-blending mixer and conditioned at 40 ° C. for 24 hours. Then the agglomerates are broken in a fast rotating agitator. The powder

  obtained is then electrostatically

  naked per se, on a phosphatized iron sheet, in a layer thickness of about 60 / u, and fired at 200 ° C. for 20 minutes. The coating does not come off the support in case of mechanical stress

manual.

  Without addition of the polymer powder according to Example 3.2, the coating can be easily detached from the phosphate iron plate.

Example 4

  4. Preparation of the dispersion 2 g of ammonium peroxydisulfate and 0.4 g of the sodium salt of an adduct prepared from triisobutylphenol and 7 mol of ethylene oxide (at 50%, commercial designation : Hostapal BV Concentrate of the Farbwerke Hoechst AG) are dissolved

  at 80 C in 400 g of water, in a pot of Witt equipped with a refrigerator

  reflux manager, a stirrer and a flow addition vessel. To this solution is added drop by drop under

  stirring over a period of 4 hours, an emulsion prepared previously

  from 730 g of methyl methacrylate, 200 g of

  butyl methacrylate, 50 g of N-acrylol-2-amino-2-methyl-

  propane sulphonic acid, 20 g of itaconic acid, 10 g of thioglyco-

  2-ethylhexyl late, 19.6 of the above-mentioned emulsifier and 615 g

  of water. After completion of the flow addition, the

  It is maintained for a further 2 hours at 80 ° C., cooled to room temperature and filtered through a filter cloth.

  fine mesh of stainless steel.

  the dispersion has a solids content of 49.7 S.

Particle diameter: 178 nm.

4.2 Drying the dispersion

  The procedure is as indicated in Example 1.

  White, non-glassy pearls are obtained; main fraction, 14 15 / um. Vitrification temperature, Tg:

 C about.

  4.3 Production of the preparation of -olymers and coating

  11 parts by weight of PMIMA (binder) powder, polymetallic

  methyl crylate from RUhm GmbH, pro-

  commercial product PLEXIGUM M 914e, Bulk density: 380 g / 1 grain size: D50 = 100 / ud: 150, parts by weight of benzyloctyl phthalate, 8 parts by weight of bis (methylcyclohexyl) phthalate,

  30 parts by weight of chalk (smaller particle size)

above 90 / u for 95%),

  9 parts by weight of polymer powder according to the

  4.2 are homogenized in a roll mill and applied in the state of pasty mass, in the form of cords, on a sheet of

  iron coated with synthetic material by cataphoretic treatment.

  After gelling this mass for 10 minutes at 180 ° C., the result is a strong viscoplastic sealant which adheres

remarkably well to the support.

  Without using the polymer powder according to Example 4.2 above, the gelled material can be detached easily

of the support.

Example 5

  5.1 Preparation of the dispersion 0.3 g of ammonium peroxydisulfate and 0.6 g of C15 paraffin sulphonate (commercial designation: Emulsifier K30, Bayer AG) are dissolved at 80 ° C. in 1200 g of water in a pot de Witt (6 l) equipped with reflux condenser, stirrer and flow addition vessel. To this solution, an emulsion prepared beforehand from 2550 g of sodium methacrylate is added dropwise with stirring over a period of 3 hours.

  methyl, 330 g of butyl methacrylate, 120 g of N-vinyl-

  imidazole, 14.4 g of the above-mentioned emulsifier, 0.9 g of the initial

  mentioned above and 1820 g of water. After completion of the addi-

  By flow, 0.3 g of the aforementioned initiator is added and the batch is stirred for 2 hours at 800 ° C. After cooling to room temperature, filter through a filter cloth

  fine mesh of stainless steel.

  the dispersion has a solids content of about 50 g. 5.2. Drying the dispersion

  The procedure is as indicated in Example 1.

  Vitrification temperature, Tg = about 90 ° C., 5.3 Production of the polymer preparation and coating 48 parts by weight of saturated polyester resin (based on

  esters of terephthalic acid and of

  multifunctional cools), melting range: 60 - 115 C, softening zone: 55 - 60 C, 7red: approx. 0.25, OH number: approx. 120, parts by weight of TiO2 (rutile type) are mixed homogeneously at 140 ° C. in a kneader with

  forced mixing and, after cooling to room temperature

  crushed in the form of fine powder (<60 / u). 15 parts by weight of a polymerization product according to Example 5.2 for parts by weight of this mixture are homogeneously incorporated therein, in a fast-rotation mixer, and the product obtained is electrostatically applied, so known per se, in a layer thickness of about 25 / u on a

  phosphated iron and cooked at 2000 C for 15 minutes.

  The coating, subjected to manual mechanical stresses,

does not come off the support.

  Without addition of the polymer powder according to the example

  5.2 above, the coating can be detached easily from the support.

Claims (13)

  1. Polymer preparations for coating substrates,   having improved adhesion, based on suitable polymers   for coating, characterized in that they contain polymers P suitable for coating and 5 to 50% by weight, based on the polymers P, of adhesion-promoting HP polymerisation products which consist of: for from 0 to 100% by weight, of at least one monomer of formula I Ra CH2 = C - X (I)   wherein R 1 is hydrogen, alkyl of 1 to 6 carbon atoms in straight or branched chain or phenyl and X has the following meanings: ## STR2 ## ZY being set for an oxygen atom or for -NR2 (R2 being a   hydrogen atom or an alkyl radical with 1 to 6 carbon atoms   n), Q for a hydrocarbon chain with 1 to 10 carbon atoms, optionally branched or for a cyclic radical with 5 to 10 carbon atoms and Z for a group - CH - CH 2; -0-CH2-O-CH3; - (OCH2CH2) mOR'2; N0 / - (OCH2-CH2) m - NR3R; - (OCH 2 CH 2) m - N; -S 03H2; -O-C - Q '- COOH   in which R'2 and Q 'have the same meanings as R2 and   that Q, m is set to 0, 1 or 2 and in which R3 and R4, inde-   pendently of each other, are hydrogen or optionally branched alkyl radical, or R3 and R4 form, with nitrogen, a 5- or 6-membered heterocyclic ring which may contain nitrogen or oxygen atoms or 2) - (CH2) n -R5 n being 0, 1 or 2 and R5 being set for a group of 0 O   mule - C - Y '- Bs; - C - Bs or -Bs, in which Y 'has the   same meaning that Y and Bs represents a heterocyclic group   containing one or more rings and having at least one nitrogen atom in the ring, and B) for 0 to 99.5% by weight of monomers of formula II R7 H2C - C - R8 (II)   wherein R7 is hydrogen or methyl.   and R8 for a -COOR9 radical, where R9 is an alkyl radical optionally   cyclic to 1 - 10 carbon atoms, or R8 is put   for a phenyl radical optionally substituted with radicals   alkyl groups with 1 to 4 carbon atoms, and C) for from 0 to 10% by weight of monomers of formula III HOOC - A - 000CH (III)   in which A represents a radical with 2 to 12 carbon atoms   containing at least one double bond in the Q 'position relative to the carboxyl group and / or the internal anhydride or cyclic imide derived from the dicarboxylic acids of formula III, with the proviso that the sum of the monomers A) plus B) s still at least 90% and up to 100% by weight of the adhesion promoting HP polymerization product and the vitrification temperature of the HP polymerization product   promoting adhesion is in the range of 40 to 15000 C.   2. Polymer preparations according to claim 1, characterized in that   characterized in that the adhesion-promoting HP polymerization products have an average molecular weight X in the range from 5,000 to 500,000.   3. Polymer preparations according to claim 2, characterized in that   characterized in that the adhesion-promoting HP polymerization products have an average molecular weight in the range of 000 to 200 000.   4. Polymer preparations according to any one of the   1 to 3, characterized in that the polymer products   adhesion-promoting HP are implemented under the form of a dried dispersion.   5. Polymer preparations according to any one of the   1 to 4, characterized in that the polymer products   adhesion-promoting HP are implemented under the   form of a spray-dried dispersion.   6. Polymer preparations according to any one of the   1 to 5, characterized in that the polymer products   adhesion-promoting HP is carried out in the form of particles, with an average particle size in the range of 0.05 to 5 μm.   7. Polymer preparations according to any one of the   1 to 6, characterized in that the polymer products   HP adhesion promoter exhibit a structure with core and envelope.   8. Polymer preparations according to any one of the   Claims 1 to 7, characterized in that the known polymers P suitable for coating are chosen from the group of polymers and copolymers of CPV, polyamides, polyesters,   polyolefins, fluorinated hydrocarbons, acrylic resins, epoxy, alkyds, amino.   9. Polymer preparations according to any one of the   1 to 8, characterized in that they are suitable for powder coating.   10. Polymer preparations according to any one of the   1 to 8, characterized in that they are suitable for plastisol coating.   11. Process for the production of polymer preparations for coating substrates having improved adhesion   based on known polymers, suitable for coating,   characterized in that 5 to 50% by weight, relative to the polymers P, of adhesion-promoting HP polymerization products which consist of:   A) for C to 100% by weight of at least one monomer of formula the Ri1 CH2 = C - X (I)   wherein R 1 is hydrogen, an alkyl radical of 1 to 6 carbon atoms in a straight or branched chain or a phenyl radical and X has the following meanings: ## STR2 ## ZY being set for an oxygen atom or for -NR2 (R2 being a   hydrogen atom or an alkyl radical with 1 to 6 carbon atoms   n), Q for a hydrocarbon ring with 1 to 10 carbon atoms, optionally branched or for a cyclic radical with 5 to 10 carbon atoms and Z for a group - Cv - C 0C R - C / -2H 2; - -O-CHCH3; (OCH2CH2) m0R'2; on - (OCH 2 -CH 2) m - NR 3 R 4; - (O4H2CH2) m CN; -S03H; -OPO3HR'2; 2 -OC - Q '- COOH   in which R'2 and Q 'have the same meanings as R2 and   that Q, m is set to 0, 1 or 2 and in which R and R4, inde-   pendently of each other, are put for a hydrogen or an optionally branched alkyl radical or R3 and R4 form, with nitrogen, a 5- or 6-membered heterocyclic ring which may contain nitrogen or oxygen atoms, or (2) - (CH2) n-R5   n being equal to 0, 1 or 2 and R5 being set for a group of 0 0   II I! mule - C - Y '- Bs; - C-Bs or -Bs, in which Y 'has the   same meaning that Y and Bs represents a heterocyclic group   containing one or more rings and having at least one nitrogen atom in the ring, and B) for 0 to 99.5% by weight of monomers of formula II H2C C - R 8 H2C C 8 (II)   wherein R7 is hydrogen or methyl   and R8 for a -COOR9 radical, where R9 is an alkyl radical optionally   cyclic to 1 - 8 carbon atoms, or R8 is put   for a phenyl radical optionally substituted with radicals   alkyl groups with 1 to 4 carbon atoms, and C) for from 0 to 10% by weight of monomers of formula III HOO0 - A - COOH (III)   in which A represents a radical with 2 to 12 carbon atoms   containing at least one double bond at position t with respect to the carboxyl group and / or the internal anhydride or cyclic imide derived from the dicarboxylic acids of formula III, with the proviso that the sum of the monomers A) plus B) is always at least 90% c and up to 100% by weight of the adhesion promoting HP polymerization product and the vitrification temperature of the HP polymerization product   promoting adhesion is in the range of 40 to 150 C.   12. Process for the powder coating of supports,   in the use of polymer preparations according to Claims 1 to 9.   13. Process for plastisol coating of supports,   in that using polymer preparations according to Claims 1 to 9.