DE2222401A1 - METHOD FOR PRODUCING IMPRAEGNATED CARRIER MATERIALS FOR SURFACE COATING - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our reference: OZ 29 153 Mu / Ja 6700 Ludwigshafen, 5.5.1972

Process for the production of impregnated carrier materials for surface coating

The invention relates to an improved. Method of manufacture impregnated carrier materials for surface coating, in the case of paper or a paper similar material with an aqueous Aminoplast condensate impregnated and preferably on the impregnated material a one-sided layer of an acrylic ester copolymer is applied without intermediate drying.

It is known, monochrome or printed with decorative patterns papers, fleeces or textile fabric webs with thermosetting To impregnate aminoplasts or phenoplasts from aqueous or aqueous-alcoholic solution and then the webs obtained to dry. The materials obtained are used for the production of laminates (laminates in the narrower sense) and for production used by surface coatings for wood-based materials. The resin-impregnated material webs are used from pressure and heat on a suitable surface, such as B. a chipboard, a fiber or plywood board, a phenolic resin-impregnated carrier layer or applied to mineral carriers such as asbestos panels and connected to the base. This type of material production is of great importance.

It is also known to have aminoplasts and phenoplasts in the portrayed One after the other in the so-called double soaking process or to be applied to carrier webs in a mutual mixture.

Similar developments (mostly in the form of unsupported films or sheets) based on thermoplastic polymers such as polyvinyl chloride, for example, have been tried but have not

641/688/71 309846/102? " ⁸ -

Gained importance.

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It is now known that aminoplastic coatings are If suitable processing techniques are used, they are characterized by high gloss and great hardness. With aminoplastic binders solidified surfaces, even when called an aminoplast Melamine resin is used, however, with prolonged exposure the free atmosphere has not been shown to be permanent. So it is z. B. not possible with melamine resin; coated materials to be used for outdoor applications. However, phenolic binders that largely meet these requirements are as is well known, not light-colored and therefore ruled out for decorative outdoor applications.

It is therefore an object of the invention to propose a method with the help of which carrier materials impregnated with aminoplastic binders are produced for surface coating which, because of their weather resistance, are also suitable for outdoor use.

There are also coatings whose binders consist of melamine-formaldehyde condensates is built, cannot be produced with the short pressing times that would be possible on the apparatus side, especially leaves the gloss of the surfaces with shorter pressing times. A recooling of the press plates is not possible with short press times possible. It was therefore a further object of the invention to propose impregnation systems that relate to the processing method allow maximum economic efficiency (i.e. short pressing times, correspondingly low heating and cooling energy consumption) and yet achieve the highest known quality standard of coated surfaces (high gloss, hardness, crack resistance, cohesion).

According to the invention, the objects are achieved in that one

a) in a manner known per se, carriers with an aqueous preparation of a thermosetting aminoplast precondensate treated,

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b) optionally intermediate drying and

ο.ζ. 29

c) a solution or dispersion of a formaldehyde condensate compatible with one side of the carrier substances treated in this way and thermosetting acrylic ester copolymer as well as'

d) if appropriate, drying and, if appropriate, pressing in the heat.

In the context of the invention, aminoplast precondensates are to be understood as meaning, in addition to urea resins, preferably melamine-formaldehyde precondensates. Melamine-formaldehyde precondensates are z. B. obtained in a known manner by subjecting melamine and formaldehyde to the condensation in an alkaline aqueous solution, the molar ratio between melamine and formaldehyde generally being selected between 1: 1.8 and 1 ϊ j5. Melamine can be completely or partially replaced by urea, with appropriate adaptation of the molar ratio and the production conditions.

The production conditions for aminoplast impregnating resins which are required for carrying out the invention are in general known. In this respect, reference can therefore be made to the relevant publications.

The acrylic ester copolymers to be used according to the invention the following is to be said in detail:

Thermosetting acrylic ester copolymers compatible with formaldehyde condensates - Just like the aminoplast condensates already mentioned - are known per se; Descriptions of suitable copolymers are, for. B. contained in Hölscher, Reinhard, dispersions synthetic plastics (series: Chemistry, Physics and Technology of Plastics in Individual Representations, Vol. 13 and 14, Berlin, Heidelberg, New York 1969). It is advantageous to choose those copolymers which are water-dilutable or water-dispersible; In principle, however, it is also possible to use those copolymers which can be applied from organic solution.

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As the name Acrylestercopdlymerisate indicates, is more essential A constituent part of these copolymers are in each case at least one ester of acrylic acid. Esters of methacrylic acid are equivalents to consider acrylic esters. Polymerizable or copolymerizable esters of (meth) acrylic acid with monohydric, z. B.

Alkanols containing 1 to 8 carbon atoms accordingly form the essential constituent of those which can be used according to the invention Copolymers. In detail z. B. methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate. The esters mentioned can - at least partially - be replaced by their technical equivalents, such as. B. styrene or Acrylonitrile or other polymerizable vinyl compounds, which also form hard films and are used to build such copolymers suitable. The abovementioned monomers are generally in the copolymers with a proportion of 10 to 98 percent by weight included. For economic reasons, the aforementioned monomers usually make up a proportion of 50 to 90 percent by weight in the copolymers.

Water dilutability or water dispersibility is that according to the invention copolymers to be used generally by polymerizing in up to 25 percent by weight, in particular

2 to 15 percent by weight of a z. B. 3 to 10 carbon atoms, #ti -olefinically unsaturated carboxylic acid or a basic one Lent groups containing copolymerizable, olefinically unsaturated monomers. These ionizable monomers give the Copolymers according to the invention often also have a corresponding compatibility with aminoplast condensates. Examples of monomers of the last-mentioned type are for example acrylic acid, methacrylic acid, crotonic acid, maleic acid half-esters, also vinyl pyridine, vinyl imidazole, Diethylaminoäthylacrylat, etc. The copolymers formed with these monomers are polyelectrolytes and are in generally dispersible in water through appropriate salt formation or soluble, depending on the number of their ionizable groups and the composition of the aqueous liquor.

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The copolymers also contain monomers with themselves or with aminoplast condensates present at the same time Can enter into networks; such monomers carry as functional groups z. B. the epoxy group, one optionally carboxamido group substituted by methylol or methylol ether groups, an acetoacetate, vinyl or allyl group. In the group of the last-mentioned monomers also includes esters of acrylic or methacrylic acid with a more than monovalent one Alcohol, such as B. butanediol monoacrylate and its homologues.

The abovementioned group “monomers with reactive substituents” can technically form up to 85 percent by weight of the copolymer according to the invention; in general, for economic reasons, their proportion by weight is not more than about 1 to 35 %.

In contrast to acrylate resins, the z. B. contain methylolamide groups and are referred to as self-crosslinking, require acrylate resins with other reactive groups for crosslinking, i.e. heat curing, usually a low molecular weight auxiliary substance.

Such resins contain in the polymer chain, for. B. alcoholic hydroxyl groups and then require a methylolated, optionally etherified aminoplast-forming compound as a reaction partner. Hexamethoxymethylmelamine and dimethylurea, for example, are practical in use as a crosslinking aid.

Copolymers containing the special comonomers mentioned above contained in a suitable combination and which can be crosslinked with themselves or with aminoplast precondensates when heated, are for the implementation of the invention described below special meaning; they show z. B. molecular weights between 500 and 2,500 and allow relatively concentrated liquors to be produced. In general, it is possible to apply the second layer according to the invention to the carrier materials previously impregnated with aminoplasts to be applied in a single operation if one uses and ensures relatively low molecular weight copolymers,

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that this is achieved by a suitable reaction during thermal curing pass into corresponding high polymer, infusible compounds.

Preferably used copolymers of the type described above have z. B. the composition given below:

a) 1 to 98, in particular

50 to 90 percent by weight of polymerized units
at least one ester of (meth) acrylic acid with a
Monohydric alcohol containing 1 to 8, in particular 1 to 5 carbon atoms, or their technical equivalents,

b) 1 to 48, in particular 5 to 35 percent by weight polymerized .Units of a monomer of the groups specified below:

b,) N-methylol (meth) acrylamide or one of its ethers with a Monohydric alcohols containing 1 to 10 carbon atoms,

b ₂ ) polymerizable monomers containing free alcoholic hydroxyl groups, which were obtained in particular by reacting acrylic acid or methacrylic acid with a
at least dihydric alcohol with 2 to 20 carbon atoms,

c) up to 25, in particular 2 to 15 percent by weight polymerized Units of a C-olefinically unsaturated carboxylic acid having 3 to 10 carbon atoms or or and a copolymerizable one having basic groups olefinically unsaturated monomers.

Copolymers, which are suitable for the production of water-thinnable Solutions within the meaning of the invention are particularly suitable, contain z. B.

% of units of a) 40 to 98, in particular 70 to 90 wt.
Esters of (meth) acrylic acid with 1 to 8 carbon atoms
containing monohydric alkanol,

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b ₁ ) 2 to 50, in particular 5 to 35% by weight of polymerized units of monomers containing heat-crosslinkable groups of the acrylamide type or its reaction products with formaldehyde and optionally their ethers on the one hand or

bp) technically equivalent amounts of free alcoholic hydroxyl groups containing monomers in conjunction with a suitable crosslinking auxiliary substance, as well as

c) is up to 25, especially up to 10 wt.% of units of a copolymerizable monomer, the ionizable functional group capable of salt formation or.

Copolymers that can be used to produce e.g. 45 to 55 Aqueous dispersions for the purposes of the invention are particularly suitable, for. B. those that. ·

a) 40 to 98, in particular 70 to 95 wt.% of units of an ester of (meth) acrylic acid with a monohydric, · 1 to 8 carbon atoms having alkanol,

of the copolymer can result in the heat-b) · 0.5 to 50, especially 0.5 to 15 wt.% of units of compounds which crosslinks and

c) up to 10, in particular up to 5 wt.% of units of a copolymerizable monomer whose funktionelle.Gruppe is ionizable or capable of salt formation.

Suitable (meth) acrylic acid esters are e.g. B. methyl acrylate, methyl methacrylate, t-butyl acrylate, ethylhexyl acrylate; of these will be -The methyl esters generally used predominantly because they are hard Be able to form films.

Monomers causing crosslinking in dispersible copolymers are used, e.g. B. (Meth) acrylamide and their

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N-methylol or N-methylol ether compounds, also acrylic half esters of diols such as butanediol acrylate, and further z. B. diallyl phthalate and other compounds containing two or more allyl radicals contain.

Dispersible copolymers of the type mentioned can also contain other hard film-forming monomers in minor amounts such as acrylonitrile, optionally also styrene and other vinyl compounds contain. However, experience has shown that the last-mentioned monomers sometimes cause yellowing and are in some Cases less recommended.

If appropriate, crosslinking compounds can be added to the copolymers or their dispersions or solutions. For example, the precondensates are aminoplast-forming compounds with formaldehyde, such as N, N'-Dimethylol-ethyleneurea, N, N'-Dimethylol-propyleneurea, N-methylol-2-methoxyethylene carbonate, hexamethylolmelamine, N, N ¹ -dimethyloluron, and also etherified or partially etherified methylolated aminoplasts, e.g. B. N, N ^! -Dimethoxymethylene urea, N, N ¹ -Dirnethoxymethylpropylenurea, N, N ^f , N '' - hexa- (methoxymethyl) melamine and others

In addition, emulsifiers are generally used to produce the dispersions necessary; This subheading includes compounds such as salts of long-chain fatty acids or sulfonic acids, sulfuric acid half-esters of Polyoxyalkylenes and their ethers, esters and phenol ethers.

The emulsifiers are generally used in amounts up to 5 % of the dispersion.

For the purposes of the invention, further auxiliaries in both solutions and dispersions z. B. lubricants and release agents, such as natural and artificial waxes and flow aids such as certain phosphoric acid esters may be useful.

The manufacture of the copolymers is not the subject of the invention. It can be done in the usual way, for example by

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Polymerization of the components in organic or aqueous solutions or dispersants, generally at elevated levels Temperature and in the presence of polymerization initiators that generate free radicals. The use of others, in the above compilation of monomers not listed in minor amounts possible without departing from the scope of the invention is left.

It is of course also possible to add polycondensable resins to the polymer preparations, in particular, for. B. urea or Mix in melamine resins.

The desired degree of polymerization of the polymers can be conventional Way through the use of regulators or correspondingly effective ones Monomers are set, which accordingly also become components of the polymer molecules.

For the - at least twice - soaking of the carrier substances in the manner according to the invention, the following information is relevant: . -.

As described above, it is first impregnated in the usual way with a solution or dispersion of an aminoplast precondensate. On an industrial scale, the carrier web is practically exclusively continuously passed through an appropriately concentrated liquor of the impregnating agent and excess quantities of the liquor are stripped off. The application (resin weight, based on paper weight) is generally 80 to 140 %.

Now it is possible without intermediate drying to use an aqueous-alcoholic solution or aqueous dispersion of an acrylic resin constructed as described on one side z. B. to be applied by pouring, kneading or by roller application, assuming that the application device is suitably adjusted, there is generally no fear that back-mixing of the various resin applications will occur. The amount of resin applied in the second coating process is between about 10 and 50 %, based on the weight of the paper. The finished coated carrier web is then

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ORIGINAL INSPECTED

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duroh hot air impingement, _o for example in a suspension dryer, deprived of the solvent or solvents.

To demarcate the invention from similar processes, the following is provided accept:

It is already known from German Auslegeschrift 1,293,017 to produce laminated bodies from papers impregnated with polycondensed resins in that the paper is impregnated in a first stage with a solution of a polycondensable resin containing polymerization plastic oil, with a certain amount of To maintain the residual absorbency of the paper, only about 5 to 15 % polymerisation plastic and about 10 to 15 % polycondensable resin are applied in the first pass; this is followed by intermediate drying and then, in a second stage, the web is again soaked with a solution containing a polycondensable resin, dried and further processed accordingly. According to a particular embodiment of this process, an addition of a polymer plastic dispersion is also added to the resin solution in the second stage. According to the description, this method is intended to solve the problem of producing particularly hard, scratch- and abrasion-resistant laminated bodies which show no tendency to crack under the influence of weathering or temperature.

Another method is described in German Auslegeschrift 1,469,570. Again, this procedure is divided into two Layers impregnated, with two melamine resin solutions in succession be applied with intermediate drying, of which the binder of the first layer has a relatively long curing time and the Binder body of the second layer have a relatively short hardening time. The German makes a similar proposal Patent specification 1 053 303, on which the aforementioned German Auslegeschrift 1 469 570 expressly refers.

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Finally, it should be pointed out that in the branches of industry that deal with the production of resin-impregnated papers, Processes are used in which, after the application of aminoplastic impregnating agents and their drying, a painting process The technique to be described is used in which the surface of the impregnated and dried paper is subsequently z. B. is provided with a layer of a nitrocellulose lacquer. This is also usually followed by drying.

With the known methods described above, however, one can do not produce resin-impregnated paper webs that. after pressing On an appropriate base, coatings result with which wood-based materials are sustainable from the effects of the weather can be protected. They also do not allow the use of shortened pressing times or working without recooling on the press.

Production of acrylic esters that can be used according to the invention

copolymers

a) 2,200 parts by weight of water are mixed with 20 parts by weight of a 15% strength aqueous solution of an Na salt of lauryl sulfonic acid and 35 parts by weight of ammonium persulfate heated in a polymerization vessel to 80 ° C.

A mixture of 2,200 parts by weight of water, 247 parts by weight of a 15% aqueous solution of an Na salt of lauryl sulfonic acid, 100 parts by weight of a 50% aqueous solution of a mixture of saturated and unsaturated alkyl sulfates, * with 12 to 18 Carbon atoms, 4,580 parts by weight of methyl methacrylate _} 120 parts by weight. Acrylic acid and 120 parts by weight of acrylic acid amide run into the polymerization vessel within about 2 hours.

After completion of the polymerization is cooled and a. Mixture of 500 parts by weight of a 20% ester wax ■ emulsion, 35 parts by weight of 25% aqueous ammonia solution

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and 20 parts by weight of a leveling surfactant (available under the trade name ^ tingal A) added.

b) 1,200 parts by weight of water, 10 parts by weight of a 15 $ igen aqueous solution of Turkish red oil, 10 parts by weight of a 15 $ aqueous solution of a sodium salt of lauryl sulfonic acid and 18 parts by weight of ammonium persulfate are in a Given the reaction vessel and heated to 85 ° C.

A second vessel, a mixture of 1380 parts by weight water, 3OO parts by weight of a 15 ^ aqueous solution of a sodium salt of Laurylsulfosäure, 100 parts by weight of a I5 $ aqueous solution of Turkish red oil, I35 parts by weight of a 45 follow aqueous solution of N-methylolmethacrylamide , 60 parts by weight of acrylamide, 2,700 parts by weight of methyl methacrylate, 120 parts by weight of 3-chloro-2-hydroxypropyl acrylate and 60 parts by weight of acrylic acid are supplied within 3 hours. The heating is then carried out for a further 30 minutes, any remaining monomer residues are removed and then cooled.

270 parts by weight of a 20% solution are added to the cold dispersion aqueous emulsion from ES wax BASF, 5 parts by weight of 25% ammonia and 5 parts by weight of the defoaming and leveling agent Etingal A stirred in. A 45-50% dispersion is obtained.

c) 2 "400 parts by weight of water, 20 parts by weight of a 15 $ aqueous solution of Turkish red oil, 20 parts by weight of a 15 ^ aqueous solution of a sodium salt of Laurylsulfosäure and 36 parts by weight of ammonium persulfate are added to a reaction vessel and heated to 85 ⁰ C.

A mixture of 2760 parts by weight of water and 500 parts by weight of a 15% aqueous solution is obtained from a second vessel of a sodium salt of lauryl sulfonic acid, 300 parts by weight a 15 $ aqueous solution of Turkish red oil, 5,700 ge

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parts by weight of methyl methacrylate, 120 parts by weight of acrylic acid and ΐ8θ parts by weight of acrylamide supplied within 3 hours. The heating is then carried out for a further 30 minutes, any remaining monomer residues are removed and then cooled.

540 parts by weight of a 25% aqueous emulsion from SS-Wachs BASF, 10 parts by weight of 25% ammonia, 600 parts by weight of a 50% aqueous solution of Ν, Ν'-dimethylolethyleneurea and 8 parts by weight of the antifoaming and leveling agent Etingal are added to the cold polymerization dispersion A mixed in.

A 45-50 % stable dispersion with a pH value between 4 and 5 and with good spreadability is obtained.

d) 300 parts by weight of water, 2 parts by weight of a 15 $ aqueous solution of Turkish red oil, 2 parts by weight of a 15 ^ aqueous solution of a sodium salt of Laurylsulfosäure and 2.5 parts by weight of ammonium persulfate are added to a reaction vessel and heated to 85 ⁰ C. A mixture of 260 parts by weight of water, 35 parts by weight of a 15% aqueous solution of a sodium salt of lauryl sulfonic acid, 25 parts by weight of an aqueous solution of Turkish red oil, 450 parts by weight of methyl methacrylate, 60 parts by weight of butyl acrylate, 12 parts by weight of acrylic acid are obtained from a second vessel , 18 parts by weight of acrylamide and 60 parts by weight of diallyl phthalate supplied within 3 hours. The heating is then carried out for a further 30 minutes, any remaining monomer residues are removed and then cooled.

45 parts by weight of a 20 aqueous emulsion of ES wax BASP, 2 parts by weight of 25% ammonia and 1.2 parts by weight of the defoaming and leveling agent using Etingal A and βθ parts by weight of a 50% aqueous solution of Ν, Ν are added to the cold dispersion -Dimethyloläthylenurea stirred in. An approximately 45% stable polymer dispersion is obtained.

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example 1

With a - based on the dry content - 55 ^ igen aqueous Solution with a viscosity of 35 cP of a storage-stable melamine-formaldehyde condensate with a molar ratio of melamine too

Formaldehyde of 1: 1.8 wild a 110 g / m heavy decorative paper made of high-grade cellulose in an impregnation plant with 110% - based on paper weight - resinated,

2 Without intermediate drying, JO g / m an impregnation solution, consisting of

5 kg of a 50 follow butanolisehen acrylic resin solution 0.5 kg of dimethylethanolamine

7.5 ^ g water

5 kg melamine impregnating resin (55 ^ Ig in aqueous solution)

Applied homogeneously on the top. It is then dried in a flotation dryer (circulating air temperature 150 ° C.) to 6 % volatile content. The surface protection film produced in this way is pressed on both sides in a known manner for 6 minutes on both sides of a weatherproof bonded chipboard at a pressure of 18 kg / cm and a temperature of 145 ° C.

Example 2

2
A 110 g / m heavy decorative paper is mixed with a condensate,

phenol

produced by condensation of / melamine and formaldehyde, pre-impregnated. After leaving the first impregnation unit, the resin application, based on the weight of the paper, is 120 %. It is then dried to a volatile content of 12%.

With an intermediate impregnator, 30 g / m 2 of a thermally crosslinkable 55% strength aqueous butanolic solution of a methacrylic ester copolymer are applied to the top. At 140 ° C., volatile components are then dried to 6%.

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The otter surface protection film produced in this way is applied to a fungus-protected weatherproof glued chipboard at a pressure of 18 kg / cm and a temperature of l45 C β minutes in known Way pressed on both sides.

A release paper against the pressure plates (brass, nickel-plated and chrome-plated) is not required.

Example 3

The pre-impregnation of 110 g soda kraft paper is used carried out with a mixed condensate of melamine, phenol and formaldehyde as in Example 2.

2 Without intermediate drying, 30 g / m 2 of a thermally curable aqueous dispersion of a methacrylic ester copolymer (55%) are applied to the top. The further treatment and compression of the film corresponds to Example 2 ₀

Comparative experiment to example 3

With an aqueous solution of a melamine-formaldehyde condensate (Mo! Ratio of melamine to formaldehyde 1; 1.8; viscosity ·] 50 cP) based on the dry content τ 52 $, decorative paper made of fine pulp in an impregnation system with 145 % - based on the weight of the paper - resin.

Hereinafter, dried in a flotation dryer with an air circulation of 150 ⁰ C to volatile to ^ 5y% of play. The melamine resin film produced in this way is on a weatherproof chipboard at a

ρ
Pressure of 20 kg / cm and egg:

pressed on in a known manner.

Pressure of 20 kg / cm and a temperature of l45 ° C for 5 minutes in

The following table shows the improved properties of the surface protective films;

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Synthetic resin water vapor permeability Atlas Weatherome outdoor exposure - permeability of the austerest ρ ration under -, hardened synthetic resin test result) 45 ° inclination ^) films ¹ ) Yellowing chalk

(g per square meter and day)

Comparative experiment

1
2

6.5 5.0

4.5

4th 1 beginning
Surfaces
damage 2 0 unchanged 0 0 unchanged 0 0 unchanged

The impregnated films are pressed without a chipboard support using the data given for the lamination examples. Measuring conditions: measuring temperature: 20 ⁰ C, moisture gradient 85% /

0 % rel. F. according to DIN 53 122

'' After 400 hours: yellowing: 0 no yellowing - 5 strong yellowing chalking: 0 no chalking - 5 strong chalking

->' After 1 year

Example 4

2
A white decorative paper of 100 g / m 2 is soaked in an aqueous solution, based on the dryness content, of a melamine-formaldehyde condensation resin with a molar ratio of melamine: formaldehyde 1: 2.5 and a viscosity of 35 cP. The dry resin application after leaving the first impregnation bath is 110% based on the weight of the raw paper atro. The resin application increases asymmetrically towards the rear.

Without intermediate drying, a directly connected

2. Impregnation system a 50% dispersion according to a) applied on the top

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gen. The applied layer is homogeneously distributed over distribution rollers. Then it is dried in a flotation dryer with circulating air to a proportion of volatile constituents of 5 * 5 %.

The dry resin application from the 2nd application stage is 30 g / m.

The processing of the film is then shown in Example 6.

Example 5.

A white decorative paper of 100 g / m 2 is as in Example 3

impregnated.

After a short drying time with an infrared heater, a
50 % dispersion according to c) applied on top. The hung up
The layer is homogenized over distribution rollers, then dried to 4.5% volatile constituents. The dry resin application

from the second stage is 25 g / m.

Example 6

A decorative paper of 100 g / m 2 filled with 25 % titanium dioxide is then impregnated as described in Example 5, but with a resin application of 115 % _t based on the weight of the raw paper.

After intermediate drying in the flotation dryer to a content of
volatile fractions of 25 % is a mixture consisting of 75 parts by weight of the dispersion from b) and 25 parts by weight of the
Melamine-formaldehyde impregnating resin from Example 3 applied to the top. The applied layer is smoothed over distribution rollers; then the web is guided plane-parallel through a flotation dryer and dried to 5.0% volatile constituents. In the second application stage, '
designated mixture.

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2
In the second application stage, 35 g / w solid resin were obtained from the above

The following table shows the processing data and the quality characteristics of the end faces.

Synthetic resin films
from example
4 5 35 6th no attack Melamine .. \
Resin film ' visible 190 Pressing time sec. 35 170 45 240 + 180 20th Press plate
temp. C. 170 15th 170 150 no Pressing pressure kg / cm . ² .15 no 15th 20th frosted Recooling no high
shiny. no Yes easy
porous shine high
shiny. pores
free shiny. glittering 1 Closed
Ness pores
free 0 pores
free easy
porous Impact Prone to cracks
according to Be
burden
DIN 53 799 0 0 1 Acid test with 1 η
Hydrochloric acid in An
based on DIN 53 799

1 Ί 2

'' Decorative paper with 100 g / m resin application based on atro paper 140 % melamine-formaldehyde impregnation resin modified in a molar ratio of 1. Residual volatile content 4.8 %

2.2

'Level 0; Decorative surface unchanged up to level 4: Trial is

torn through

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ORIGINAL INSPECTED

Claims (10)

- 19 - 'Ό.ζ. 29 153 Claims fly Process for the production of carrier materials impregnated with aminoplastic binders for surface coating, characterized in that one a) in a manner known per se, carriers with an aqueous preparation of a thermosetting aminoplast precondensate treated, b) optionally intermediate drying and c) a solution on one side of the carrier materials treated in this way " or dispersion of a formaldehyde condensate compatible and thermally curable acrylic ester copolymer brings up, as well d) if appropriate, drying and, if appropriate, pressing in the heat. 2. The method according to claim 1, characterized in that a melamine-formaldehyde precondensate is used as the aminoplast precondensate. 3. The method according to claim 1, characterized in that the acrylic ester copolymer is applied as an aqueous solution or dispersion 'wi rd. 4. The method according to claim 3, characterized in that the acrylic ester copolymer is applied without intermediate drying, 5. The method according to claim 1, characterized in that the aeryl ester copolymer - optionally together with a phenoplast or aminoplast condensate - is thermosetting. 6. The method according to claim 1, characterized in that the aeryl ester copolymer is a copolymer! Sat from ■ a) 2 to 98 percent by weight units of at least one ester of (meth) acrylic acid with a monohydric alcohol having 1 to 8 carbon atoms,
b) 1 to 48, in particular 5 to 35 weight percent polymerized 309846/1027 - 20 - ' - 20 - O.Z. 29 merized units of a monomer as detailed below designated groups; b ») N-methylol (meth) acrylamide or one of its ethers with one Monohydric alcohols containing 1 to 10 carbon atoms, bp) polymerisable alcohols containing free alcoholic hydroxyl groups Monomers that have been obtained in particular by reacting acrylic acid or methacrylic acid with a at least dihydric alcohol with 2 to 20 carbon atoms, c) up to 25 weight percent units of either a 3 to 10 carbon atoms containing polymerizable o ^ -olefinically unsaturated Carboxylic acid or or and a copolymerizable, olefinically unsaturated one containing basic groups Monomers and d) optionally up to 88 percent by weight of units of a further olefinically unsaturated copolymerizable monomer is used. 7. The method according to claim 6, characterized in that as a further olefinically unsaturated monomer b) at least a) a polymerizable compound with carboxamide groups or one of their N-methylol or N-methylol ether derivatives or b) a polymerizable ester of (meth) acrylic acid with 2 to 10 carbon atoms having at least dihydric alcohol or "one of his reaction products with at least one Epoxy group-containing compound is used. Badische Anilin- & Soda ^ FÄbrik AG 3098