DE2454296A1 - PROCESS FOR THE MANUFACTURING OF FIBER REINFORCED FLAT MATERIALS - Google Patents

Description

X) R. MÜLLER-BORE DIi ¹ L.- \ NO. ORGlSNING DIPL.-CIIRM. DR. DETJFKL · · DIPI ..- CHEM. DB. NICE

l'ATE N T ADVOCATE JE

K / S 31-48

Süd-Wast-Chemie GmbH 7910 Neu-Ulm Pfaffenweg 18

Process for the production of fiber-reinforced, flat materials

2 -

609821/0827

B KtfNCHSK SC. SISBBKTSX *. *. POSTPAOH 800.30. ΚΛΒΒΤ.

CM"

$ 245,429

The invention relates to a method of manufacture of fiber-reinforced, flat materials with a pore-free arainoplast resin surface by impregnation a flat carrier material with a urea-melamine resin containing resin impregnation solution, drying, coating the impregnated carrier material with a plasticized melamine resin and possibly containing pigments * Cover resin preparation and curing according to the continuous hot-pressing process.

In general, the invention lies in the field of the production of laminates which are used for surface treatment of chipboard or the like can be used. Such laminates are generally used for covering the surfaces and edges of panel materials, such as those used in the manufacture of furniture and furniture parts, used. The use of melamine resins as the top layer resin in such laminates results in addition to decorative effects a number of excellent surface properties, such as resistance to heat and cold water, against a number of weak acids and alkalis, abrasion resistance and resistance to the effects of temperature. The different types of laminate are made taking into account the likely use and the stress on the material treated with it is selected.

These laminates can be made continuously from thermoplastic Plastics and discontinuously made of paper treated with thermosetting resins based on those used for production Technically feasible processes are produced for decorative surfaces. In special cases can also be used as a carrier material for the paper which forms the decorative layer and is treated with thermosetting resins.

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turns that are obtained from paper that has been treated by the treatment special strength properties with chemical reagents and by using special process methods having. The traditional methods of manufacturing thermoset coating materials are now inevitable fixed to certain lengths for discontinuous operation. More recently, however, there are also newer procedures for the production of endless webs on the basis of thermosetting resins have become known, but some of them are technical are complex and uneconomical due to the use of expensive starting materials.

In addition to conventional ones, usually made up of several water-soaked products Layers of paper under high pressure in heated and recooled Laminate panels made of multi-layer presses, as for example in the magazine "Kunststoffe", Vol. 60, 1970, Issue 8, p. 498, are described, the prior art also provides processes for the continuous production of Laminates. For example, DT-OS 2 213 477 describes a process for the continuous production of a laminate described several paper or fabric-like webs impregnated with curable resins.

Furthermore, a laminate is known from DT-OS 2 151 437, made of a thermosetting or elastomeric surface material and consists of a thermoplastic carrier and can be produced in webs.

Metzeier AG, Memmingen, also sells a rollable laminate board that can be delivered in roll form, which is also pressed from several layers and manufactured using polyester resins.

All of the above and previously known products is now in common that they are made up of several impregnated layers

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are composed and that they - if their top layer consists of amino resins - an extremely complicated and require expensive hot pressing and curing device similar to the type described in DT-OS 2 213 477, or, that the curing of the aminoplast resin; layer still during of pressing the laminate onto the panel base material must be done.

The object of the invention is now to create a method for the production of a single layer of paper or a fiber-reinforced sheet material existing laminate with a pore-free curable with the help of a continuous hot pressing process Aminoplast resin surface. This is intended to be a particularly economical, Material-saving and high-quality surface protection for furniture surfaces, in particular the moisture-proof covering of chipboard edges can be achieved.

This object is now achieved by a method of the type mentioned at the outset, which is characterized in that

1) a carrier material with a weight per unit area between 50 g and 400 g / m ² with an aqueous Harz.tränklösung that

a) about 80 parts by weight of a urea known per se -Melamine-formaldehyde-diethylene glycol co-condensation product with a viscosity of 13-18 cP at 20 ° C, a resin content of about 50-2% by weight, a pH of 8.0, a solubility in water of 1:10 and a B-time at 140 ° C (300 mg) of 11-12 minutes,

b) about 4-12 parts by weight of a sulfonamide,

c) about 11-14 parts by weight of about 95% 2,4,6-tris (methoxymethylamino) -1,3,5-triazine containing etherification product from trimethylolmelamine and methanol and with - 5 - *

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d) about 1-5 parts by weight of p-toluenesulfonic acid to a gel time between 100 and 300 seconds at 98 ° C and a B time (140 ⁰ C, 130 mg) is between 5 and 60 seconds is set.

with a resin absorption of 20-80% of the weight of the non-impregnated carrier material ?, soaked and on is dried to a moisture content of less than about 5%,

2) the impregnated carrier material is coated with a cover resin preparation in an amount of about 10-100 g / m ² , which

e) about 40-70 parts by weight of one using known plasticizer of multi-stage condensed, highly plasticized melamine formaldehyde resin with a viscosity of 200-300 cP at 20 ° C, a resin content of 65-70%, a pH value of 8 - 9, a B-time (140 ° C, 400 mg) of 4-6 minutes and a solubility in water of 1: 1.8 - 1: 2.2,

f) about 20-60 parts by weight of about 95% 2,4,6-tris (methoxymethylamino) -1,3,5-triazine containing etherification product of trimethylolmelamine and methanol,

g) about 0.3-10 parts by weight of a sulfonamide and

h) about 1-10 parts by weight of a known silicone impregnation emulsion, consisting of a mixture of an aqueous polysiloxane dispersion with a 0.07-fold Weight fraction of a hydrogen polysiloxane or an aminopolysiloxane and 0.1 times Weight fraction of an organotin compound, and a solids content of about 70-80%, a pH value of 7.5-8.5 and a B-time (140 ° C,

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~ 6

300 ing) of 4-5 minutes, and

3) the coated material cures according to the continuous hot pressing process.

This process surprisingly gives a fiber-reinforced, flat material with a pore-free aminoplast resin surface, which can be glued with wet and hot melt adhesives without sanding the back, shows no change in the surface after gluing, can be easily milled without splintering the edges, has a uniform gloss and with regard to scratch resistance and chemical resistance corresponds to the standard applicable for decoratively coated chipboard. Furthermore, the material can be produced continuously as an endless strip by means of the impregnating solutions and cover resin preparations used in the present process, without a dimensional change and thus a deterioration of the surface of the carrier material occurring during curing and without the resins used leaving residues on the continuous Heated rollers applied by hot pressing process are left behind. According to the claimed process, the surface resin used can be cured without pores in a uniform layer thickness at a ^{normal temperature in the temperature range from 180 to 200 0} C in the course of 1 to 3 seconds, whereby a perfect adhesion to the substrate is achieved without the cover resin in the underlying impregnated carrier material penetrates. Furthermore, the cover resin used can easily be pigmented with conventional pigments.

According to a preferred embodiment of the invention, papers with basis weights between

2 2

see 50 g and 400 g / m, preferably about 200 g / m, used, the preferably wet tear length values of 700-900 meters

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and air permeability values of approx. 100 ml (according to Schopper) and the one on the preferably satined top layer side Smoothness values according to Beck (see "Handbook of Materials Testing", Volume 4 (Korn-Burgstaller), page 314, 2nd edition, publisher Springer, 1953) between 5 and 35 seconds, preferably 20 seconds /.

This known carrier material is with a aqueous, optionally aqueous methanolic according to the invention Impregnated resin impregnation solution, for example according to the method specified in DT-OS 2 133 820 or as follows can be produced:

One carries into one with a stirrer and a reflux condenser equipped glass bulb:

180 g formaldehyde solution (40%) 2.4OMoI (1.5-2.8)

18.6 g methanol (95%) 0.55 mol (0.15-0.6)

15 g diethylene glycol 0.14 mol (0.1-0.2)

60 g urea 1.0 mole (1.0)

15.0 g melamine 0.12 mol (0.1-0.2)

0.6 g NaOH solid 0.015 mol (0.01-0.03)

After the addition of the catalyst (NaOH), the mixture is heated to the boil and refluxed for 4 hours, a reaction product with the following properties being obtained:

Viscosity: 13-18 cP (20 ° C)

Resin content: 50 - 2% (determined at 105 ^° C.)

Weight 2 g, determination time 2 hours pH value: 8-9
Solubility: 1:10 in water
. B time: 12-20 minutes (140 ° C, 400 mg) Stability: After 4 weeks of storage at 20 ° C, the

Solution still clear in the event of an increase in

Viscosity by max. 30% ..

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The B-time or hardening time given above is based on that in the "Plastics Internship" (Gaetano D'Alelio, Carl Hanser-Verlag / Munich 1952, p. 174) described longitudinal test procedures 4 carried out, with 0.3 g of resin at the specified temperature in a well with a diameter of 2 cm and a maximum depth of 8 mm with a The tip of the pulled-out glass rod is stirred until it has hardened and the time required for this is measured.

According to the invention, 4 to 12 parts by weight, preferably, are added to 80 parts by weight of the initial impregnation solution obtained 10 parts by weight, of a sulfonamide, preferably an aromatic sulfonamide, most preferably p ~ toluene ~ sulfonamide, adding the material slurried in approximately the same amount of methanol and until it is complete Stir in solution. This measure causes, in an unexpected way, a substantial reduction in the porosity of the cured Aminoplast resin surface of the process product.

Then, according to the invention, another 11 to 14 are preferred 13 parts by weight of a known etherification product of trimethylolmelamine and methanol added, the one Has solids content of about 70% and about 95% 2,4,6-tris (methoxymethylamino) -1,3,5-triazine contains. This measure leaves with the urea-melamine condensation product described above largely and surprisingly obtained the advantages of a pure melamine resin.

The next step in the process is the resin impregnation solution obtained in this way by adding p-toluenesulfonic acid to a Gel time of 100 to 300 seconds, preferably 250 seconds, at 98 ° C and a B-time (140 ° C / 300 mg) between 5 and 60 seconds, preferably 15 seconds, set.

This measure results if the raw paper is impregnated with a resin content of between 20 and 80%, preferably 35%

-B-

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and dried, a sufficiently fast for the continuous hot press curing to a moisture content below 5% (residual moisture after 5 minutes drying oven storage at 160 ⁰ C) and at the same time a support for the surface layer of the topsheet resin without that there is an impairment of the desired pore freedom.

The impregnated carrier material shows only a slight reduction its air permeability, however, a multiplication its wet breaking length. Surprisingly, it also shows valuable properties in use due to its special properties advantageous suitability as coatable and Paintable primer film.

According to the invention, the impregnated carrier material is now with a coating resin preparation according to the invention coated. This cover resin contains a known, highly plasticized, starting resin condensed in several stages using known plasticizers, which is described in the following Way can be made:

A glass flask equipped with a stirrer and a reflux condenser is charged with a mixture of 360 g (3.60 mol) of 30% strength formaldehyde solution and 110 g (0.81 mol) of pentaerythritol, which is mixed with a mixture of 0.325 g (0 , 0017 mol) of p-toluenesulfonic acid, 0.225 g (0.007 mol) of methanol and 0.350 g (0.0027 mol) of ethyl acetoacetate to a pH of 2.5 to 3.0. This reaction mixture is heated to the boil and kept at the boiling temperature for 30 minutes. After this time the reaction is briefly interrupted by cooling to 75 ⁰ C to 80 ° C is set and then the pH is adjusted with 1 _r 5 g (0.0168 mol) of dimethyl ethanol amine to 9.0 to 9.5. 170 g (1.35 mol) of melamine, 17.5 g (0.05 mol) of sucrose and 85 g (4.72 mol) of water are then added and the mixture obtained is heated for more than about 20 minutes

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to boiling until one part of resin can be diluted with 15 to 20 parts of water. After the reaction has been interrupted again by cooling, this is added
Reaction mixture with a further 100 g (0.793 mol) of melamine
and 40 g (0.40 moles) of a 30% formaldehyde solution. After heating to the boil, the reaction will last for 15 to
Continued for 40 minutes until a solubility in water of 1: 1.8 to 1: 2.2 is reached. The subsequent dehydration under reduced pressure is terminated after a viscosity of 300 to 400 cP has been reached, after which 40 g (1.25 mol) of methanol are added to the reaction mixture.
The resin, cooled to 20 ° C, has the following properties:

Viscosity: 200-300 cP

Resin content (2 hours, 100 ⁰ C): 65% - 70%

B-time (140 ^° C., 400 mg): 4-6 minutes

pH value: 8-9

Solubility in water: 1: 1.8 to 1? 2.2.

According to the invention, 20 to 60 parts by weight, preferably 50 parts by weight, of an etherification product containing about 95% 2,4,6-tris (methoxymethylamino) -1,3,5-triazine are added to 40 to 70, preferably 65 parts by weight of this starting resin Trimethylolmelamine with methanol, which has a solid resin content of 70%, and gives 0.3
up to 10 parts by weight, preferably 7 parts by weight, of a sulfonamide, preferably an aromatic sulfonamide, most preferably p-toluenesulfonamide, with this addition also - if this is for decorative effects
it is desirable - suitable fillers, eg 5 - 60% titanium dioxide, can be stirred in.

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By adding the etherification product of trimethylolmelamine and methanol and the sulfonamide is cured while maintaining the excellent performance properties of the cured Aminoplast layer largely avoids porosity and brittleness of the material.

Finally, according to the invention, the cover resin preparation is added still with 1-10 parts by weight, preferably 2 parts by weight, a known silicone impregnation emulsion, consisting of a mixture of an aqueous polysiloxane dispersion (silicone impregnation emulsion E 322 from Wacker · Chemie GmbH) with 0.07 times the weight fraction of a hydrogen polysiloxane (VP 1084) or an aminopolysiloxane (VP 1543) with 0.1 times the weight fraction of an organotin compound (VP 1515).

The cover resin preparation obtained in this way does not have the otherwise feared tendency to stick to the heated surfaces of the continuously operated hot-pressing device.

After adjustment to a solids content of 70-80%, a pH of 7.5-8.5 and a B-time (140 ° C., 300 mg) of 4-5 minutes, the cover resin preparation obtained is applied using a customary application device, e.g. a doctor blade, in a suitable layer thickness (for example in a

2
ner application quantity of 10-100 g / m) and, if necessary, with the use of curing aids on the impregnated carrier material. After the coated carrier material has cured, which is carried out continuously using conventional hot pressing devices, for example rotating, heated metal rollers, one of which can optionally be provided with an embossing pattern to form a surface structure, only one layer of fiber-reinforced material is obtained

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Laminate comprising flat material with a pore-free aminoplast resin surface.

The viscosities given are with the Höppler viscometer determined according to DIN 53015.

In view of the state of the art, it must be regarded as surprising that the combination the measures according to the invention and in particular the resin impregnations and cover layer resin extensions used with the help of known impregnation and coating methods, using thin, only single-layer Carrier material Laminates with pore-free aminoplast resin surface to obtain pools that have high-quality properties.

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Claims (12)

K / S 31-48 Süd-West-Chemie GmbH Neu-ülm Pfaffenweg 18 patent claims 1. Process for the production of fiber-reinforced, fluffy. Materials with a pore-free aminoplast resin surface by impregnating a flat carrier material with a urea-melamine resin containing Resin impregnation solution, drying, coating of the impregnated Carrier material with a plasticized one Melamine resin and, if necessary, pigments containing top coat preparation and curing according to the continuous hot pressing process, characterized thereby e t that 1) a carrier material with a basis weight between 50 g and 400 g / m with an aqueous Plarz impregnation solution, the a) about 80 parts by weight of a known urea-melamine-formaldehyde-diethylene glycol co-condensation product with a viscosity of 13-18 cP at 20 ° C., a resin content of about 50-2% by weight, a pH of 8.0 , a solubility in water of 1: TO ι
12 minutes, of 1: TO and a B-time (140 ⁰ C, 300 mg) of 11- - 14 609 821/08 27 b) about 4-12 parts by weight of a sulfonamide, c) about 11-14 parts by weight of an about 95% 2,4,6-tris (methoxymethylamino) -1,3,5-triazine containing etherification product of trimethylolmelamine and methanol and with d is set) about 1-5 parts by weight of p-toluenesulfonic acid to a gel time between 100 and 300 seconds at 98 ⁰ C and a B time (140 ° C, 130 mg) is between 5 and 60 seconds, with a resin uptake of 20-80% of the weight of the non-impregnated Carrier material is soaked and dried to a moisture content of less than about 5%, 2) the impregnated carrier material is coated with a cover resin preparation in an amount of about 10-100 g / m ² , which e) about 40-70 parts by weight of a highly plasticized melamine-formaldehyde resin condensed in several stages using known plasticizers with a viscosity of 200-300 cP at 20 ° C, a resin content of 65-70%, a pH value of 8 -9, a B time (140 ^° C., 400 mg) of 4-6 minutes and a solubility in water of 1: 1.8-1: 2.2 f) about 20-60 parts by weight of about 95% 2,4,6-tris (methoxymethylamino) -1,3,5-triazine containing etherification product of trimethylolmelamine and methanol,. g) about 0.3-10 parts by weight of a sulfonamide and h) about 1-10 parts by weight of a known silicone impregnation emulsion, consisting of a mixture of an aqueous polysiloxane dispersion with a 0.07-fold weight fraction of a hydrogen polysiloxane - 15 - 609821/0827 or an aminopolysiloxane and 0.1 times Weight fraction of an organotin compound, and a Fcststoffgeha.lt of has about 70-80%, a pH value of 7.5-8.5 and a • B-time (140 ° C, 300 mg) of 4-5 minutes, and 3) the coated material is cured by the continuous hot pressing process. 2. The method according to claim 1, characterized in that 1) a carrier material with a weight per unit area of approx 2
200 g / m with an aqueous Hars.tränklösuxKj that a) about 80 parts by weight of a known urea-melamine-formaldehyde-diethylene glycol co-condensation product with a viscosity of up to 18 cP at 20 ° C, a resin content of about 50 - 2% by weight, a pH value of 8.0, a solubility in water of 1:10 and a B-time (140 ° C, 300 mg) of 11-12 minutes, b) about 10 parts by weight of a sulfonamide, c) about 12.5 parts by weight of an about 95% 2,4,6-tris (methoxymethyl ^, amino) Containing -1,3,5-triazine Etherification product from trimethylolmelamine and methanol contains and with d) about 2.5 parts by weight of p-toluenesulfonic acid a gel time of about 250 seconds at 98 ° C and a B-time (140 ° C, 130 mg) of about 20 seconds is set, with a resin pick-up of about 35% of the weight of the impregnated carrier material and dried to a moisture content of about 1.5-4% will, - 16 609 8 2 1/0827 2) the impregnated carrier material 'is coated with a cover resin preparation in an amount of about 10-100 g / m ² , which e) about 40-70 parts by weight of a multi-stage plasticizer using known plasticizers condensed, highly plasticized melamine-formaldehyde resin with a viscosity of 2OO - 3OO cP 20 ° C, a resin content of 65-70%, a pH value of 8-9, a B-time (140 ° C, 400 mg) from 4 to Minutes and a solubility in water of 1: 1.8 to 1: 2.2, f) about 50 parts by weight of about 95% 2,4,6-tris (methoxymethylamino) -1,3,5-triazine containing etherification product of trimethylolmelamine and methanol, g) about 5-7 parts by weight of a sulfonamide and h) about 2 parts by weight of a known silicone impregnation emulsion, consisting of a mixture of an aqueous polysiloxane dispersion with a 0.07-fold proportion by weight of a hydrogen polysiloxane or an aminopolysiloxane or with a 0.1-fold weight proportion of an organotin compound, contains, and a solids content of about 70-80%, a pH of 7.5-8.5 and a B-time (14Q ° C, 300 mg) of 4-5 minutes, and 3) the coated material is cured by the continuous hot pressing process. 3. Process according to Claims 1 or 2, characterized in that p-toluenesulphonamide is used as the sulphonamide. 4. Process according to Claims 1 to 3, characterized in that a urea-melamine-formaldehyde-diethylene glycol mixed condensation product a is used, which after a - 17 - 609821/0827 drive is available, which consists in that one about 1.5-2.8 moles of formaldehyde in the form of a 40% aqueous solution, about 0.15-0.6 moles of 95% methanol, about 0.1-0.2 moles of diethylene glycol, about 1.0 mole of urea, about 0.1-0.2 moles of melamine and about 0.01-0.03 moles of solid NaOH at a pH of over 10 for .4 hours to boiling reflux until solubility in water 1:10 is reached. 5. The method according to claim 4, characterized in that a urea-melamine-formaldehyde-diethylene glycol co-condensation product a is used, which is obtainable by a process which consists in that one about 2.40 moles of formaldehyde in the form of a 40% strength aqueous solution, about 0.55 moles of methanol (95%), about 0.14 moles of diethylene glycol, about 1.0 mole of urea, about 0.12 mol ^ melamine and
about 0.015 moles of solid NaOH at a pH of over 10 to boiling for 4 hours reflux until a solubility in water of 1:10 is reached. 6. The method according to claims 1 to 5, characterized in that that a highly plasticized melamine-formaldehyde resin e is used, which can be obtained by a process is, according to which a mixture of about 3.6 moles of formaldehyde (in the form of a 30% aqueous solution) and about 0.81 mol pentaerythritol with a mixture of about 0.0017 moles of p-toluenesulfonic acid, about 0.007 moles of methanol - 18 609821/0827 - 1b and about 0.0027 mol of ethyl acetoacetate to a pH of 2.5 to 3.0, the mixture is brought to reflux for 30 minutes, the reaction is interrupted by cooling to 75 ⁰ C to 80 ⁰ C, the reaction mixture with about 0.0168 mol dime thy läthano'lamin on
adjusts a pH of 9.0 to 9.5, adds about 1.35 mol of melamine, about 0.05 mol of sucrose, about 4.7 mol of water, the reaction mixture for about 20 minutes or more at the boiling temperature up to one Water ·· - thinnability of one part of resin in 15 to 20 parts of water further converts the reaction by cooling
75 ⁰ C to 80 ⁰ C interrupts the reaction mixture
about 0.793 mol of melamine and about 0.40 mol of a 30% strength aqueous formaldehyde solution are added, the reaction is continued at the boiling point until a solubility in water of 1: 1.8 to 1: 2.2 is reached, the reaction product under reduced Pressure drained until a viscosity at 20 ° C of 300-400 cP is reached and the obtained
About 1.25 moles of methanol are added to the product. 7. The method according to claims 1 to 6, characterized in that the carrier material _{used is a paper filled or unfilled with TiO 2} , kaolin or the like, which has a basis weight of about 50-400 g / m ² , an air permeability of 100-500 ml (according to Schopper) and on the top layer side has a smoothness value according to Bekk of 5-35 seconds. 8. The method according to claim 7, characterized in that a paper is used that has a basis weight of - 190-200 g / m ² , a wet tear length of 700-900 m, one
Air permeability value of approx. 100 ml (according to Schopper) and on the satined top layer side a smoothness value according to Bekk of approx. 20 seconds. - 19 - 609821/0827 9. The method according to claims 1 to 8, characterized in that the cover resin preparation used Contains 4-50% pigment. 10. The method according to claim 9, characterized in that a titanium dioxide pigment is contained as the pigment. 11. The method according to claims 1 to 10, characterized in that that the curing takes place in that the impregnated and coated material, if necessary after pre-drying under the action of heat, continuously between two heated, rotating metal rollers using a line pressure through it . to be led. 12. Use of the fiber-reinforced, flat, pore-free obtained according to the preceding claims Materials for coating the surfaces of chipboard or similar substrates. 609821/0 827