DE2755589A1 - Modified aminoplastics used in wood and laminate coating - is modified with condensate of caprolactam, formaldehyde and formamide - Google Patents

Abstract

Modified aminoplastics is modified with 0.5-40 pref. 2.5-15 wt.% condensate (I) of epselon-capro-lactam, HCHO and form -amide, pref. in 1:a:b molar ratio (in which a = 1-20, b = 1-19 and a/(b+1)=0.5-1). The aminoplastics is used specifically for the inpregnation of paper and textiles used for the mfr. of coated wood prods, or laminates by preessing wood at 10-100 bar and 120-180 degrees C or phenolic resin-impregnated kraft paper at 50-150 bar and 120-180 degrees C. It has satisfactory storage properties.

Description

ADDITIONAL TO:

NAME: Aminoplast, process for its manufacture and its Use for the preparation of coated wood materials or laminates the Invention relates to a modified aminoplast, which is particularly suitable for impregnation of paper or fabric webs in the production of coated wood-based materials or laminates. The invention also relates to a method of production of the modified aminoplast and its use for the production of coated Wood-based materials or laminates.

Aminoplasts are resinous products and their solutions that are made by Condensation of compounds containing amino or imino groups, the so-called Aminoplast formers and carbonyl compounds and optionally a lower alkanol develop.

The reaction between the aminoplast formers, the carbonyl compounds and optionally the alkanol is only carried out to the extent that the products still remain soluble and fusible.

As soon as this state is reached, the condensation is canceled, e.g. by cooling and adjusting the reaction mixture to a weakly alkaline pH. The non-condensed aminoplasts produced in this way (also known as aminoplast precondensates called) are in the form of their aqueous solutions, especially as impregnating resins for the laminate industry and for surface finishing of wood-based materials used.

When it comes to the surface finishing of wood-based materials, wood fiber or chipboard a decorative or protective layer is applied in that decorative Paper or fabric webs with suitable aminoplasts, preferably melamine resins, soaked and with a certain residual moisture content on the panels of the wood material be laminated by thermosetting. The pressure 2 can be about 10 to 100 bar (1 bar = 10 Pa: lkp / cm2) and the temperature is around 120 to 1800C. During the pressing process, the aminoplast hardens and connects the paper or Fabric sheet with the panel of the wood-based material. Laminates can be used in a similar way Manufacture with a decorative or protective surface. Here, the aminoplast resin is soaked Decorative sheet on several layers of phenolic resin-impregnated kraft paper Thermosetting pressed on. The pressing pressures are in the range from about 50 to 150 bar, while the pressing temperatures as in the case of decorative coating in front of wood materials, for example 120 to 180 0C. To increase the scratch and abrasion resistance, before the Press a so-called aminoplast resin-soaked, transparent, onto the decor sheet Overlay paper applied.

Sometimes there is also a barrier paper between the decor sheet and liters and a backing paper for use on the back.

For the impregnation of the overlay and the decor sheet, preferably Melamine-formaldehyde resins for use. Even with the surface finishing of Wood-based materials, overlay and barrier papers can be used.

Coated wood materials and laminates are characterized by their good chemical and physical properties. The for the watering the for the Do not use the paper or fabric webs provided for the decorative or protective layer However, elasticized aminoplasts have only a small amount in the cured state Elasticity, which is why top stitches made with these resins tend to crack.

There has been no lack of attempts, the lack of elasticity of the decorative layer to be eliminated or reduced by adding to the impregnating resins. In particular Additives were polyalcohols, sorbitol and sugar, as well as aromatic sulfonamides recommended. However, when polyalcohols or sugars are added, the water resistance becomes lower of the cured resins is insufficient if the elasticity is to be sufficient. Sulphonamides alone are not enough to achieve good elasticity.

When the aminoplasts are processed, there is a transition to the soluble ones and fusible aminoplast precondensates into infusible and insoluble products. Crosslinking occurs during this hardening process. The speed of this crosslinking reaction However, even at the elevated processing temperatures, it is for technical applications Processes too few and must therefore be accelerated by adding so-called hardeners will. As a hardener acidic and / or acidic releasing agents Connections used. Such harders are, for example, ammonium or amine salts, e.g. ammonium chloride, ammonium rhodanide, ethanolamine hydrochloride or strong organic Acids such as p-toluenesulfonic acid. When using free acids or strong acidic salts result in relatively short pot lives for the aminoplast resin, thereby affecting processing.

With an addition of caprolactam as modiLizierungsmittel for the The impregnating resins can increase the elasticity of the finished surfaces proportionally high amounts of hardener can be added while still having a sufficiently long service life can be achieved before use. However, the unsatisfactory one is not very good Reserve of elasticity, reduced water resistance and uneven shine of the surfaces produced with it.

Impregnating resins, which are suitable for the addition of large amounts of hardener or hardening accelerators Additives and therefore suitable for particularly rapid hardening or processing, are referred to in the broadest sense of the word as "short-cycle resins" and have themselves conquered a large market in a short time.

It is known (DT-OS 21 49 970) that cracking in the surface of wood-based materials and laminates eliminated or their elasticity increased can be, if the for the decor or. Protective layer provided paper or Fabric webs impregnated with an aminoplast resin modified with methylenebisformamide and then laminated onto wood-based panels in a manner known per se or processed into a laminate. Even when using methylenebisformamide-modified Aminoplast resins as so-called short-cycle resins result in a more uniform formation Gloss of the coated surfaces.

In practice, however, it has been shown that with prolonged storage methylenebisformamide-modified aminoplast resins their application advantages, in particular the crack resistance, is partly lost again.

It has now been found that in the surface finishing of wood-based materials and the production of laminates flawless surfaces using a sufficiently storable aminoplast resin can be obtained if the for the Decor or

Protective layer provided paper or fabric web with an inventive Aminoplasts soaked and then in a known manner on the Ilolzwerkstoffplatte laminated or processed into a laminate.

The aminoplast according to the invention is characterized by a content from 0.5 to 40% by weight, preferably 2.5 to 15% by weight, based on the solids content of the finished resin, on a condensation product of -Cnprolactam, formaldehyde and formamide resp.

the reaction products of the condensation product with the resin formers. In particular, in the case of the condensation product used as a modifier the molar ratio 6-caprolactam formaldehyde: formamide = 1: a: b, where a is a Number from 1 to 20 and b represents a number from 1 to 19 and a and b are selected as such be that the quotient a = 0.5 is 5 to 1. The numbers a need b + 1 and b not necessarily to be an integer. Molar ratios are particularly preferred 6-caprolactam: formaldehyde: formamide = 1: (1 to 2): 1.

An aminoplast former is used to produce an aminoplast according to the invention in a manner known per se with a carbonyl compound and optionally others Modifying agents, such as water-soluble alcohols, condensed and before or during or, after the condensation, a condensation product of 8-caprolactam, formaldehyde and formamide, especially with the molar ratio 6 -caprolactam: formaldehyde: Formamide = 1: a: b, where a is a number from 1 to 20 and b is a number from 1 to 19 represents and a and b are chosen so that the quotient a = 0.5 to 1, b + 1 preferably 1: (1 to 2): 1, adds.

The preparation of the condensation product required as a modifier from to -caprolactam, formaldehyde and formamide can be done, for example, in such a way that Formamide and paraformaldehyde in Presence of an alkali hydroxide 4 to 15 hours is heated to temperatures of approx. 800C with stirring. Afterward the reaction mixture is made acidic, for example by adding potassium hydrogen sulfate, and the -Caprolactam added and the batch heated to 100 to 135 ° C and, if necessary under a vacuum of approx. 100 to 300 mbar, the result of the condensation Water is distilled off, the use of an entrainer such as toluene, is appropriate. The & -caprolactam can also be added at the beginning of the reaction will. The condensation products obtained after the entrainer has been distilled off are mostly clear viscous liquids that in all proportions with water are miscible and have little tendency to crystallize even in the undiluted state.

With a molar ratio of g-caprolactam: formaldehyde: formamide = 1: 1: 1, the production of the modifier produces a product which is in pure crystalline form as N- (formylaminomethyl) -caprolactam of the formula can be isolated. With a molar ratio of C c-caprolactam formaldehyde: formamide = 1: 2: 1, the methylolation product of N- (formylaminomethyl) - & - caprolactam, namely N- (N'-formyl-N'-hydroxymethyBaminomethyl) - £ -caprolactam, the formula can be isolated in pure form. The compound of the formula I represents the best modifying agent according to the invention, followed by the compound of the formula II. However, it is not necessary to purify the compounds of the formula I or II for their use as modifying agents or to isolate them in pure form, but rather it is sufficient if the oily raw products obtained during manufacture are used to manufacture the aminoplast resin.

The starting products for the production of aminoplasts are the known aminoplast formers, such as urea, hiourea, dicyandiamide, guanamines, such as aceto- or benzoguanamine, but especially melamine and the condensation with aminoplast formers known carbonyl compounds, which are aliphatic and aromatic aldehydes and ketones, such as i3. Acetaldehyde, butyraldehyde, i-butyraldehyde, Acetone, methyl ethyl ketone, etc., but especially formaldehyde, can be considered. Even Mixtures of aminoplast formers and / or carbonyl compounds can be used to produce of the aminoplast. Are melamine-formaldehyde condensation products particularly preferred, but also condensates of formaldehyde, melamine and others Aminoplast binder, in particular urea, as well as mixtures of amine-formaldehyde condensates and condensation products of formaldehyde and other aminoplast formers, in particular urea, have proven particularly useful for the production of resins according to the invention.

That according to the invention to be used for the modification of the aminoplast Condensation product of 8-caprolactam, formaldehyde and formamide can be used before, during or added to the resin to be modified after the aminoplast condensation has ended will. Normally, 0.5 to 40 wt.%, Preferably 2.5 to 15 wt., Are related based on the solids content of the finished resin.

The condensation product to be used as a modifier -Caprolactam, formaldehyde and formamide can also be added in the form of aqueous solutions will. When using a condensation product t-caprolactam: formaldehyde : Formamide = 1: 1: 1, or the compound I, the addition is expedient towards the end of the condensation, preferably after the condensation to the cooled one has ended Resin solution. It is also possible to use part of the condensation product used for modification from 2-caprolactam, formaldehyde and formamide at the beginning of the resin condensation add and the rest during or after the condensation admit. If a condensation product with the molar ratio t-caprolactam: formaldehyde : Formamide = 1: 2: 1, or the compound II is used, it is advantageous first to produce the condensation product from caprolactam, formaldehyde and formamide and after subsequent addition of the aminoplast former and the carbonyl compound to carry out the condensation of the resin. The condensation product is added from r - aprolactam formaldehyde: formamide before or during the condensation of the resin, then normally at least a part reacts with the resin formers.

After the condensation has ended, the aminoplasts according to the invention also hardeners or hardening accelerators, e.g. salts of weak to strong organic compounds Acids, for example diethanolaminoacetate, ethanolamine hydrochloride, ethylenediamine acetate, Ammonium rhodanide, ammonium lactate or ethylenediamine phosphate can be added to to accelerate the hardening process without affecting the elasticity of the coatings worsened.

Other modifiers can also be used in the manufacture of the resins, such as water-soluble mono- or di-alcohols, e.g.

Methanol, ethanol, ethylene glycol, ethylene diglycol, also pentaerythritol, Carbamates, such as methyl carbamate, methoxyethyl carbamate, salts of the maleic or Fumaramic acid, sugar, sorbitol, salts or sulfamic acid, aromatic sulfonic acid amides and the like can be added.

In the resin production, as usual, the condensation only goes so far carried out that the resins still remain soluble and meltable. The Usually condensed up to a limited water dilutability. In some cases, E.g. when larger amounts of salts of sulfamic acid are added, the obtained Resins also have unlimited water solubility. To determine the water thinnability a sample of the resin is titrated with water at 200C. E.g. the indication says "Water dilutability 1: X", that 1 ml of resin can absorb X ml of water at 200C, without turbidity occurring. Notes on the implementation of the condensation in the production of aminoplasts are contained, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, 1st Edition, Vol. 1 (1947), 756-759; Houben-Weyl "methods of organic chemistry ", Vol. XIV / 2," Macromolecular substances ", Part 2, (1963), Georg Thieme Verlag Stuttgart, in particular pages 346 to 357 (urea condensates), Pages 357-371 (melamine condensates), pages 382-388 (condensation products of Dicyandiamide and guanidine); John F. Blais "Amino Resins", Reinhold Publishing Corp., New York (1959), pp. 2G-53; C.P. Vale "Aminoplastics" Cleaver Hume Press Ltd., London (1950), pages 12-87; Ullmann's Encyclopedia of Technical Chemistry, 4th edition, Volume 7 (1973), pages 403-414.

The production of decoratively coated wooden panels using the aminoplasts according to the invention takes place in such a way that the paper or Fabric web impregnated with an aminoplast according to the invention and known per se Way is further processed. The soaked and dried paper or fabric web is thus on the prepared wood-based panel under printing from approx. 10 to 100 bar and temperatures of approx. 120 to 1800C, whereby for the pressing multi-daylight presses are advantageously used. Analog can be used when using of carrier sheets impregnated with phenolic resin instead of the wood-based panels Laminates are produced, with pressures of about 50 to 150 bar and temperatures from approx. 120 to 1800C are used. Notes on the manufacture of coated Wood-based panels and laminates can be found in J.F. Blais loc cit, pp 122-138; C.P. Vale loc cit, pages 209-214, and Ullmann loc cit, pages 417 - 418.

The laminates produced using aminoplasts according to the invention and coated wood-based materials show a high uniform gloss, flawless Curing and high elasticity and also meet the rest, to a flawless Surface demands made. The aminoplasts according to the invention are storage-stable, i.e. the excellent results obtained when processing the aminoplasts will be throughout life of the resin achieved. Particularly good results are obtained when using the compound of formula I for the preparation of aminoplasts. Even when using the compound of formula II achieved very good results. The compounds of the formula I and II can also be used in impure form or in the form of mixtures, for example in the form of a condensation product from lactam: formaldehyde: formamide = 1: 1: 1 or 1: 2: 1 or 1: (1 to 2) : 1 can be used. Will be more with the production of the modifying agent Used as 1 mole of formamide, mixtures are formed. In these mixtures are the compounds of the formula I and / or II in addition to other reaction products, for example contain formamide and formaldehyde. If the conditions are right, it can Mixture also contain methylenebisformamide, for example. In contrast to aminoplasts, those modified with methylenebisformamide retain those modified according to the invention Aminoplasts, however, maintain their good properties throughout their lifespan at. The aminoplasts according to the invention are also excellently suitable as short-cycle resins and are moreover also against over-hardening, as in practice e.g. can occur due to extended press downtimes and / or increased press temperatures can, largely insensitive.

The high surface elasticity achieved with the inventive Laminates made from aminoplasts and coated wood-based materials are e.g. responsible for ensuring that when testing for susceptibility to cracks in accordance with DIN 53 799 of May 1975, number 4.7.1 (laminates), or 4.7.2 (coated wood-based materials), the samples are stored for 20 hours at 80 ° C, no cracks appear. (This determination of the susceptibility to cracking is hereinafter referred to as tempering or tempering test called.) Even when the temperature is increased to 900C occur in most There are no cracks yet.

Unless otherwise stated, percentages are given in the examples Weight percent; Temperatures are given in Celsius.

Example 1 Preparation of a Modifying Component with a Molar Ratio f-caprolactam: formaldehyde: formamide = 1: 1: 1.

225 g formamide, 2g KOH and 170 g Granuform (90 Siger paraformaldehyde) are stirred for 10 hours at 80.degree. Then 1.5 l of toluene, 560 g of £ -caprolactam and 6g of KIIS04 are added, and then the water of reaction (approx. 95 g) distilled off at normal pressure. The initially trained two layers go gradually clear in solution. When no more water passes over, it is used as an entrainer toluene used is distilled off. 820 g of a colorless oil remain, the is miscible with water in any ratio and in the form of the oil obtained for Production of aminoplasts according to the invention can be used.

The pure N- (formylaminomethyl) & -caprolactam can be obtained from the oil by distillation in a thin-film evaporator, Kpl mbat = 180 - 1840C. The pure N4Formylaminomethyl) - (-caprolactam crystallizes in long Crystal needles and has an mp = 480C.

Analysis: Calculated: C 57.1 H 7.1 N 16.7 found: C 57.3 Ii 7.0 N 16.4 The pure compound can also be used to produce aminoplasts according to the invention be used.

Example 2 Preparation of a Modifying Component with a Molar Ratio C'-caprolactam: formaldehyde: formamide = 1: 5: 9.

695 g formamide, 195 g caprolactam, 285 g Granuform (90 of a paraformaldehyde) and 1 g of KOH are stirred for 6 hours at 80 ° C., then 4 g of KHSO4 are added and about 90 ml of water of reaction are distilled off at 100 ° C. and a pressure of 266.6 mbar. 950 g (80%) of a clear, viscous liquid are obtained, in every ratio is miscible with water and also in the undiluted state.

has little tendency to crystallize.

Example 3 Preparation of a Modifying Component with a Molar Ratio C: -Caprolactam: formaldehyde: formamide = 1:10:19.

400 g formamide, 60 g t-caprolactam, 165 g Granuform (90% paraformaldehyde) and 10 g of KOH are stirred at 80 ° C. for 6 hours. Then 2.5 g of p-toluenesulfonic acid are added and 600 ml of toluene are added and the water is distilled off azeotropically. hen no water more passes over, the toluene is distilled off, finally in a water jet vacuum. Man receives in practically quantitative yield an oil which is used to modify aminoplasts suitable is.

Example 4 3250 g of 39% strength by weight aqueous formaldehyde, 300 g of methanol, 250 g of water and 200 g of a 40% strength by weight aqueous solution of the sodium salt of Amidosulfonic acid, 5 g potash and 3100 g melamine are used within 30 to 40 Minutes heated to 90 ° C and at this temperature until a water dilutability of 1: 2.2 condensed (duration approx. 4 hours). The pH of the solution should be 10.0 + 0.2. After cooling to 50 ° C., this base resin becomes "400 g of the example 2 produced condensation product mixed as a modifier and with Water set to a solids content of 56% by weight. The content of the resin at Modifying agent according to Example 2 is 8.4% by weight, calculated on a fixed basis.

4.1) 0.9% by weight of the morpholine salt of para-toluenesulfonic acid was added to this resin solution as a hardener (this hardener is also used in the following examples) on solid resin, added. In the impregnating liquor mixed with hardener, an 80 g / m2 heavy white decorative paper impregnated to a final weight of approx. 200 g / m2 and dried to a residual moisture content of 5.5 to 7% by weight (5 min./1600C).

(The specification 5 min / 1600C means that to determine the residual moisture content a sample stored for 5 minutes at 1600C and from the weight loss suffered the residual moisture content was calculated.) 4.1.1) Some of the papers were then on a short-cycle press with a pressure of 18 to 22 bar at a temperature of 1550C pressed onto chipboard. The service life of the press was 60 seconds. The surfaces of the coatings exhibited a uniform gloss and good curing no cracks after tempering for 20 hours at 140 ° C.

4.1.2) Lin part of the impregnated papers was made on a short cycle press with a pressure of 18 to 22 bar at a temperature of 180 ° C. and a standing time pressed on chipboard for 3 minutes (over-hardening pressing). The surfaces of the coatings showed none with a uniform gloss and very high curing Cracks.

4.1.3) Some of the impregnated papers were printed on a multi-daylight press with a pressure of 18 to 22 bar at a temperature of 1400C on chipboard pressed on. The press time was 10 minutes. After that it was set to a temperature cooled down from 70 to 800C and demolded. The surfaces of the coated chipboard showed a uniform high gloss with very good curing and after tempering no cracks after 20 hours at 800C.

4.2) The resin solution of Example 4 was based on 1.2% by weight of hardener on solid resin, added. In the impregnating liquor mixed with hardener, an 80 g / m2 heavy paper as in Example 4.1 soaked and dried. The impregnated Papers were pressed according to Example 4.1.2. The surfaces of the papers showed with a uniform gloss and very high curing no cracks.

4.3) The resin solution of Example 4 was used for 14 days without the addition of hardener stored at room temperature (20 to 250C), then with 0.9 wt.% Harder, based on solid resin, offset. In this solution, according to Example 4.1, an 80 g / m heavy, white paper impregnated and pressed as in Example 4.1.2. The surfaces the coatings remained free from cracks with a uniform gloss and a very high degree of curing.

4.4) The resin solution of Example 4 was mixed with 0.4% by weight of hardener. After dilution with water to a concentration of approx. 52% by weight, there was in the solution an approx. 30 g / m² heavy, highly transparent overlay paper made of cellulose impregnated to a final weight of 100 to 105 g / m 2 and a residual moisture of 6.5 to 7 Ges .; dried, and a 120 g / m2 heavy decorative paper was on a Final weight of 200 to 210 g / m2 impregnated and a residual moisture content of 5.5 Total% dried.

Together with soda kraft papers soaked in phenolic resin, a Laminate made.

Structure: 1 overlay paper 1 decor paper 9 phenolic resin-impregnated kraft papers 1 release liner (siliconized paper).

Pressing was carried out for 8 minutes at 140 ° C. and a pressure of 80 bar. before After demoulding, it was cooled back to 70 to 80 ° C. The manufactured laminate board showed no cracking after the heat treatment, which was carried out at 80 ° C. for 20 hours.

4.5) Comparative example.

400 g of methylenebisformamide are added to the base resin described in Example 4 mixed in according to DOS 21 49 970 and otherwise proceed as in Example 4. To the received Resin solution was added 0.9% by weight of hardener, based on solid resin. In this watering liquor 80 g heavy paper was impregnated according to Example 4.1, dried and according to Example 4.1.2 pressed. The surfaces of the coatings showed at uniform Gloss and very high curing no cracks.

The resin solution was left without hardener for 14 days at room temperature stored and processed as above. The surfaces of the coatings showed individual cracks over the entire surface.

4.6) Comparative example.

The preparation of the resin solution according to Example 4 was carried out with the modification repeats that the modification product has been omitted. Using the Amino resin solution prepared in this way was coated as in Example 4.1.2. The surfaces of the coated chipboard show cracks all over Area.

Example 5 490 g of the modifying agent are added to the base resin according to Example 4 of Example 2 mixed in (corresponds to approx. 10 percent by weight calculated on a fixed basis). All other reaction conditions are kept constant. Was impregnated as follows: 5.1.1) The resin solution from Example 5 was 1.2% by weight of hardener on solid resin related, added. In this solution, a 80 g heavy paper according to Example 4.1 impregnated and some of the papers as in Example 4.1.2 on chipboard pressed on. The surfaces of the coatings showed a uniform gloss and very high curing over the entire residual moisture range from 5 to 8% by weight none Cracks.

5.1.2) A second part of the papers was on a short cycle press at 180 ° C. and a pressure of 18 to 22 bar and a standing time of 5 minutes. Here, too, the surfaces of the coatings showed a residual moisture range from 5 to 8 total; with a uniform gloss and very high curing no cracking.

5.2) 0.9 X hardener was added to the resin solution from Example 5.

In this impregnation liquor, a white paper weighing 80 g / m 2 according to Example 4.1 impregnated, dried and like Example 4.1.3 on chipboard pressed on. The surfaces of the coated chipboard showed very good No hardening and uniform high gloss after tempering for 20 hours at 800C Cracks.

Example 6 290 g of the modifying agent are added to the base resin according to Example 4 mixed in according to Example 2 (approx. 6% by weight calculated on a fixed basis). All others The reaction conditions are kept constant.

4.1) The resin solution of Example 6 was added 0.9 Ghz hardener and further processed as in example 4.1.2. The surfaces of the so coated Chipboard remained free of cracks in the residual moisture range of 6 to 7 total%.

4.2) 0.4% hardener was added to the resin solution from Example 6 and further processed according to example 4.1.3. Even the decoratively coated ones produced in this way Chipboard showed high gloss and good curing after tempering No cracks for 20 hours at 80 ° C.

Example 7 In the base resin according to Example 4, 145 g of the according to Example 2 described modifying agent (approx. 3 total; calculated on a fixed basis) and 70 g of diethylene glycol mixed in. All other conditions of example 4 remain constant.

7.1) The resin solution from Example 7 was based on 0.4% hardener on solid resin, added and processed according to Example 4.1.3.

The surfaces of the chipboard coated in this way show good Curing high gloss and stay at 800C even after tempering for 20 hours crack free.

Example 8 380 g of aqueous 39% formaldehyde solution, 10 g of ethylene glycol, 20 g of methanol, 10 g of sugar, 6 g of a 40% strength by weight solution of the sodium salt Amidosulfonic acid are adjusted to a pH of 10.1 and 330 with stirring g melamine added. This mixture is heated to 90 ° C. and can be diluted with water from 1: 1.5 condensed. After cooling to 50 ° C., 40 g of the modification product are obtained according to Example 2 and 150 g of water were added. The modifier content of the oil solution according to Example 2 is 5.3% by weight, based on solid resin. This resin solution will with 0.4% hardener, based on the solid resin. In this solution a 80 g / m heavy decorative paper as impregnated under 4.1 and according to 4.1.3 on chipboard pressed on. The surfaces of the chipboard coated in this way show good curing uniform high gloss and remain free of cracks after 20 hours of tempering at 800C.

Example 9 36.0 kg aqueous 39% strength by weight formaldehyde solution, 2.7 kg Diethylene glycol, 1.0 kg of methanol, 2.2 kg of the sodium salt of sulfamic acid, 3.7 kg Sugar and 15.0 kg of water are brought to a pH of 10.1 with dimethylaminoethanol placed and added 32 kg of melamine.

This mixture is diluted at 90 ° C to a water dilutability of 1: 2.0 condensed, cooled to 50 ° C. and 3 kg of the modifying agent according to the example 2 and 5 kg of water were added. The content of the resin solution, based on solid resin Modifying agent according to Example 2 is 5.6% by weight.

9.1) This resin solution was 0.9% total hardener, based on solid resin added. In the resin solution obtained in this way, a paper weighing 80 g / m 2 is made according to 4.1 impregnated and coated with the impregnated paper chipboard as in 4.1.2. The surfaces of the coated panels remain with a uniform gloss and very high curing crack-free.

9.2) The resin solution from Example ') was harder with 0.4 Gcwtvó on solid resin, added and processed further in Example 4.1.3. The surfaces the chipboard panels coated in this way show uniformity when fully cured high gloss and remain free of pores after 20 hours of tempering at 80 C.

Example 10 3200 g of formaldehyde (39 geWSige aqueous solution), 400 g Water and 200 g of a 40% strength by weight aqueous solution of the sodium salt of sulfamic acid are adjusted to a pH of 10.2 with 2 N NaOH and 3100 g of melamine and 100 g of the modification product described in Example 2 was added. Then at 90 ° C condensed to a water dilutability of 1: 4 and a further 200 g of des Modification product added. The condensation is carried out at 90 ° C. until it can be diluted with water of 1: 1.5, cools to 50 ° C. and gives another 150 g of the modification product to.

This resin is spray-dried and can therefore be stored indefinitely. The application properties are as described in Example 5.

Claims (19)

Modified aminoplast, characterized by a Content from 0.5 to 40 total%, based on the solids content of the finished resin, on a condensation product of 6-caprolactam, formaldehyde and formamide as a modifier. 2. Modified aminoplast according to claim 1, characterized by a content of 2.5 to 15% by weight of the modifier. 3. Modified aminoplast according to claims 1 to 2, characterized in that that the modifier has a molar ratio ε-caprolactam: formaldehyde: formamide = 1: a: b, where a is a number from 1 to 20 and b is a number from 1 to 19 represents a and a and b are chosen so that the quotient bl = 0.5 to 1 is. 4. Modified aminoplast according to Claims 1 to 3, characterized in that that the modifier has a molar ratio z -caprolactam: formaldehyde: formamide = 1: (1 to 2): 1. 5. Modified aminoplast according to claims 1 to 4, characterized in that that the modifier has a molar ratio of E-caprolactam: formaldehyde: formamide - 1: 1: 1 owns. 6. Modified aminoplast according to claims 1 to 5, characterized in that that N- (formylaminomethyl) - ε-caprolactam is used as a modifier. 7. Modified aminoplast according to claims 1 to 4, characterized in that that the modifier has a molar ratio of 6-caprolactam: formaldehyde: formamide - 1: 2: 1 owns. 8. Modified aminoplast according to claims 1 to 4 and 7, characterized characterized in that the N- (N'-formyl-N'-hydroxymethyl-aminomethyl) - & -caprolactam is used. 9. Modified aminoplast according to claims 1 to 8, characterized in that that it also contains other modifiers. 10. Process for the preparation of the aminoplast according to the claims 1 to 9, characterized in that aminoplast formers and carbonyl compounds in a manner known per se up to a limited or unlimited water dilutability are condensed and before, during or after the condensation as a modifying agent a condensation product of 6-caprolactam, formaldehyde and formamide in such a Amount is added that the finished aminoplast thereof, based on the solids content of the finished resin, has a content of 0.5 to 40% by weight. 11. The method according to claim 10, characterized in that the modifying agent is added in such an amount that the content thereof is based on the solid content of the finished resin, 2.5 to 15% by weight. 12. The method according to claims 10 and 11, characterized in that that the modifier has a molar ratio & -Caprolactam: formaldehyde: Formamide = 1: a: b, where a is a number from 1 to 20 and b is a number from 1 to 19 and a and b a are chosen so that the quotient b + 1 = 0.5 to 1 is. 13. The method according to claims 10 to 12, characterized in that that the modifier has a molar ratio & -Caprolactam: formaldehyde: Formamide> 1: (1 to 2): 1. 14. The method according to claims 10 to 13, characterized in that that the modifier has a molar ratio & -Caprolactam: formaldehyde: Formamide - 1: 1: 1. 15. The method according to claims 1 to 14, characterized in that that N- (formylaminomethyl) - t-caprolactam is used as a modifier. 16. The method according to claims 10 to 14, characterized in, that the modifier has a molar ratio -caprolactam: formaldehyde: formamide = 1: 2: 1. 17. The method according to claims 10 to 14 and 16, characterized in that that the methylolation product of N- (formylaminomethyl) - -caprolactams is used. 18. The method according to claims 10 to 17, characterized in that that other modifiers are added. 19. Use of an aminoplast according to claims 1 to 9 for Impregnation of paper and fabric sheets used in the manufacture of coated wood-based materials or laminates by pressing onto wood-based materials with a pressure of approx. 10 up to 100 bar and temperatures from 120 to 1800C or impregnated with phenolic resin Kraft papers under pressures of approx. 50 to 150 bar and temperatures of 120 to 1800C be used.