WO2009027385A1

WO2009027385A1 - Composite material, use of a composite material and method for producing a composite material

Info

Publication number: WO2009027385A1
Application number: PCT/EP2008/061123
Authority: WO
Inventors: Andreas Endesfelder; Katarina Rot; Christian FÜRST; Markus Machherndl; Friedl Heger
Original assignee: Ami Agrolinz Melamine International Gmbh
Priority date: 2007-08-28
Filing date: 2008-08-26
Publication date: 2009-03-05
Also published as: DE102007041438A1

Abstract

The invention relates to a composite material that can be produced by a) mixing at least one resin material with at least one second material, b) subjecting the mixed materials in a kneader to a combined rotating and lifting movement and then melting, c) compressing the mixed and melted materials and, d) guiding to a moulding tool and then hardening. The invention also relates to a method for producing a composite material.

Description

Composite, use of a composite, and method of making a composite.

The invention relates to a composite material according to claim 1, a use of a composite material according to claim 23 and a method for producing a composite material according to claim 25.

From WO 2005/00971 melamine-formaldehyde resins with a low formaldehyde / melamine ratio are known.

Further, it is known to produce composites using resins.

An object of the present invention is to provide a composite material which can be produced well by direct extrusion.

The object is achieved by a composite material that can be produced by the following steps: a) mixing at least one resin material with at least one second material, b) wherein the mixed materials in a kneading device of a combined rotary and lifting movement and a

C) subsequent compression of the blended and molten materials; d) feeding to a forming tool and subsequent hardening.

Such a composite material can be produced efficiently by direct extrusion.

It is advantageous if the at least one second material has a proportion of 20 to 85 wt .-% of the mass of having mixed materials. It is particularly advantageous if the at least one second material has a proportion of 30 to 80% by weight, in particular a proportion of 50 to 75% by weight, of the mass of the mixed materials.

The second material advantageously has at least one fraction of wood, a cellulose, an inorganic filler, a cellulose derivative, acteylated cellulose, hemicelluloses, lignin, lignin derivatives and / or modified cellulose. The materials may be in the composite e.g. be arranged in the matrix of the resin material. Advantageously, the proportion of wood in the form of wood flour, wood particles, wood granules, wood fibers and / or wood chips is present.

Furthermore, it is advantageous if the composite material comprises a proportion of additives of 0 to 30 wt .-% of the mass of the mixed materials. As additives, e.g. at least one uncrosslinked thermoplastic, at least one lubricant, a polyvinyl butyral - polyvinyl acetate -

Polyvinyl alcohol polymer, at least one polyol, at least one flame retardant, at least one pigment, at least one stabilizer, at least one polyether polyol, at least one polyester polyol, at least one catalyst, at least one UV absorber and / or at least one radical scavenger are used as such or mixtures thereof , A lubricant is used for easier extrudability.

It is advantageous if the additive used is a mixture of uncrosslinked thermoplastic and lubricant in a proportion of not more than 5% by weight of lubricant and a proportion of uncrosslinked thermoplastic of not more than 10% by weight, based in each case on the mixed materials. Particularly advantageous embodiments are when for lubricants at least one hydrocarbon wax, at least one oxidized hydrocarbon wax, at least one zinc stearate, at least one calcium stearate, at least one magnesium stearate or other metal soaps and / or mixtures of these substances are used.

Advantageously, a pressure of less than 1000 bar is applied during the compression of the materials. It is also advantageous if the sliding properties of the mixed and melted materials are such that the pressure difference between the compression and the shaping is less than 1000 bar, in particular less than 500 bar.

In a further advantageous embodiment of the present invention, the at least one resin material has a proportion of 15 to 60 wt .-% of the mixed materials. It is particularly advantageous if the at least one resin material has a proportion of 20 to 40% by weight of the mixed materials.

The resin material may include at least a portion of a resin (e.g., a resin having a carbonyl compound), a proportion of a resin solution, a proportion of a resin emulsion, a proportion of a resin dispersion, and / or a portion of a resin melt. Examples of carbonyl compounds are aldehydes (e.g., formaldehyde, acetaldehyde, isobutyaldehyde) or ketones (e.g., acetone, methyl ethyl ketone, diethyl ketone) each having at least one carbonyl group.

A particularly advantageous embodiment is when the at least one resin material comprises or consists of at least one aminoplast. Examples for aminoplast resin formers are melamine, urea, dicyandiamide, guanamines, guanidine, guanidine derivatives, biguanide, biguanide derivatives, substituted melamines and / or substituted ureas.

Furthermore, it may be advantageous if the resin material based on urea, guanidine, aminoplasts, triazine, acrylic, phenol, polyester, melamine, epoxy, alkyd, a lignin polymer and mixtures of these substances. Base in the present context means that the resin material is manufactured using one of these materials or can be produced. In addition to the main resin components, other monomers, carbonyl compounds and / or resins may also be present.

It is particularly advantageous if at least one resin material is present on the basis of melamine and / or urea, in particular based on a melamine and / or urea-formaldehyde resin.

Advantageous variants are when the at least one melamine and / or urea-formaldehyde resin is an etherified resin and / or a partially etherified resin and / or an unetherified resin and / or if the at least one

Resin material is a modified, unetherified melamine and / or urea-formaldehyde resin or an unmodified unetherified melamine and / or urea-formaldehyde resin.

The composite has particularly good properties when at least one resin is an unmodified, unetherified melamine and / or urea-formaldehyde resin, which can be prepared with a molar ratio of formaldehyde to amino component of less than or equal to 1.5. Advantageously, the composite material is present as a plate, profile or tube. Advantageous forms of use are windows, doors, cladding elements and roof elements in the outdoor area, as well as in the sports and leisure sector for garden furniture, outdoor seating and playground design.

The object is also achieved by a method having the features of claim 25, wherein

a) at least one resinous material is mixed with at least one second material, b) the mixed materials are subjected in a kneader to a combined rotating and lifting movement and reflowing, c) subsequently the mixed and melted materials are compressed and d) a shaping tool are supplied and hardened,

The combined turning and lifting movement ensures that, in combination with the melting, a particularly good mixing of the materials takes place in axial (by the lifting movement) and radial direction.

It is advantageous if the mixing and the melting takes place in a screw shaft device, in particular with at least one CoKneter. Advantageously, the worm shaft device is designed as a direct extrusion. Direct extrusion, in particular, combines the two processes of compounding and molding into a single process step. A separate compounding step (semi-finished product production) is eliminated. In a further advantageous embodiment of the method according to the invention, the molten material is conveyed by at least one pumping device through a profile tool. It is particularly advantageous if the pumping device has at least one gear pump, at least one single-screw extruder and / or at least one twin-screw extruder.

Advantageously, the dosage of at least one of the components in the screw shaft device in the form of individual components or in the form of a produced free-flowing mixture of the individual components. It is advantageous if the component mixtures or individual components are conveyed via an inlet screw into the co-kneader, into the kneading agent and / or the mixing agent.

Advantageously, the wood, the resin materials, in particular melamine resins and / or the additives in the at least one kneading agent, the at least one mixing agent and / or the at least one CoKneter melted homogenized, and degassed and then promoted the mixture to a melt pump. Particularly advantageous are melamine resins, which essentially have a shear-dependent viscosity.

Advantageously, the melting process for the components is started by rotation speeds of the kneading agent and / or the mixing agent from 80 U / min to 200 U / min. For starting the temperatures of the CoKneterschnecke advantageously from 20 ⁰ C to 100 ⁰ C and the temperatures of CoKnetermanteltemperierzonen of 60 ⁰ C to 160 ⁰ C set. Advantageously, the melt pump is flanged via a transition piece to the CoKneteraustrag, and it is particularly advantageous if a start-up opening is integrated in the transition piece.

Furthermore, it is advantageous if the high-pressure melt pump brings the pressure build-up of 50 to 1000 bar to the profile tool.

In a particular method are advantageously

a) the wood, melamine resins and additives in CoKnetermanteltemperierzonen of about 60 to 160 ⁰ C and screw temperatures of 20 to 100 ⁰ C melted, homogenized and degassed,

b) the mixture at a mass temperature of about 80 ⁰ C to 200 ⁰ C is compressed,

c) then introduced with elevation of temperature to 110 to 300 ⁰ C in a forming tool, in which the crosslinking takes place, and

d) the finished composite material discharged.

Embodiments of the invention will now be described by way of example with reference to the figures. Show it:

Fig. 1 shows an embodiment of a discontinuous

Carrying out a process for producing a melamine resin in a stirred tank; Fig. 2 shows an embodiment of a continuous

Carrying out a process for producing a melamine resin in the tubular reactor;

Fig. 3 is a sectional view of a first embodiment of a co-kneader for producing a composite material;

Fig. 4 is a sectional view of a second embodiment of a co-kneader for producing a

Composite material.

In the following the invention will be described by way of examples. It will first be described (Figures 1 and 2), e.g. Melamine - formaldehyde resins or resin solutions can be produced. This resin or resin solution is but one example of a resinous material that can be used to make a composite of this invention. Also, resin materials e.g. based on other aminoplast or other carbonyl compound can be used.

Furthermore, it will be described by means of some examples how embodiments of the composite materials can be produced (FIGS. 3 and 4).

Preparation of the resin material

In Fig. 1, formaldehyde 1 (ie, a carbonyl compound) is preheated in the preheater 2 to the target temperature (eg, mixing temperature Tm). Melamine (ie an aminoplast generator) and water 4 are introduced into the discontinuous stirred tank 6 and there to the target temperature (eg Mixing temperature Tm) is heated. The required amount of liquor is presented in Laugedosierbehälter 5 in solution. Once the formaldehyde and the melamine-water mixture have reached the desired temperature, the valves 3 are opened, formaldehyde and the liquor under pressure to the melamine-water

Mixture metered in the stirred tank 6 and the reaction mixture with the mixing temperature T _m produced.

Here, therefore, a resin material based on melamine and formaldehyde is used as an example so as to later produce a composite material (see FIGS. 3 and 4). The reaction is conducted at T _m until the clear point is reached. It is then further condensed to the desired water compatibility, either maintained the temperature T _m or by lowering the heating in the stirred tank 6, a lower condensation temperature T _{k is} set. After reaching the desired resin properties, the resin solution is cooled and then the melamine-formaldehyde resin solution is discharged at the bottom of the stirred tank 6 (discharge 7). The melamine-formaldehyde resin solution can be converted into a storage-stable resin powder by spray-drying.

Another embodiment is shown in FIG. In this case, melamine, formaldehyde, water and alkali 11 are continuously conveyed in the desired mixing ratio in the tempered and stirred suspension vessel 12. Melamine is dosed as a solid, while water, formaldehyde and lye are conveyed as a liquid mixture in the container. Stirring stabilizes the suspension. The pH of the suspension is monitored with a pH electrode and with a Laugedosierpumpe kept constant. The suspension is withdrawn continuously at the bottom of the suspension tank 12 by a metering pump 13 which pumps the suspension to the required pressure in the tubular reactor 14, in which a plurality of separate heating circuits

Temperature profile is set. The exiting at the bottom of the tubular reactor 14 melamine-formaldehyde resin solution is cooled by the cooler 15 to room temperature and discharged via the expansion valve 16 17.

The drying of the resin solution can advantageously be achieved by spray drying. Conventional spray drying uses an air flow into which the warm or even cold resin solution is introduced. The drying of the resin solution can also be achieved by means of flash drying. The warm resin solution is dried under relaxation (pressure reduction) without air. To assist in drying, an air stream can also be introduced during flash drying.

Examples 1 to 3:

The experimental conditions of Examples 1 to 3 are shown in Table 1.

37% formalin solution is heated in a heatable receiver tank to the mixing temperature T _m . At the same time, melamine and water in the reactor are also heated to the mixing temperature T _m with vigorous stirring in suspension. The KOH is dissolved in 250 ml of water and placed in a small pressure vessel (Laugedosierbehälter) on the reactor. After the formalin solution and the melamine suspension have reached the temperature T _m The formalin solution and the dissolved KOH added under pressure of the melamine suspension at the same time. The dosing process is completed after approx. 2 minutes. The suspension is then stirred to the clear point under autogenous pressure at the temperature T _m . After the suspension has clarified to the solution (clear point) is further condensed until the desired water compatibility of the resin solution at the condensation temperature T _k and then the resin solution is cooled to room temperature. The resin solution is cooled to below 100 ^° C. after about 5 minutes and to room temperature after about 20 minutes.

To characterize the resin solutions the water compatibility at 20 ⁰ C, the stability of the resin solution in a clear state at room temperature and the pH are determined. The composition is determined by means of HPLC / UV / MS, the proportions of melamine, sum of the monomers, sum of the dimers and sum of the trimers and oligomers are determined. The water compatibility is given in [ml of water per ml of resin] and refers to the amount of water that can be added to the resin solution at 20 ^° C. before permanent haze of the resin occurs.

Examples 4 and 5, continuous process:

The experimental conditions of Examples 4 and 5 are shown in Table 2.

37% formalin solution, melamine, water and KOH are metered continuously into a suspension vessel, which is tempered at the mixing temperature T _m , melamine with a gravimetric solids dosage, formalin, water and KOH together as a solution with a liquid dosage be dosed. Stirring keeps the suspension stable. The pH of the suspension is maintained between 9.6 and 9.8. With a metering pump, the suspension is brought to pressure p and pumped at a throughput D in the tube reactor. The tubular reactor consists of the series-arranged parts of the pre-reactor of volume Vol _v and the post-reactor of volume VOI _N. The prereactor is heated electrically, the secondary reactor is tempered by means of temperature control. In the prereactor, the suspension is heated in the heating time t _a to the reaction temperature T _r . The heated suspension then passes into the post-reactor with the condensation temperature T _κ . In the postreactor, the suspension is then clear and the resin solution is further condensed within the condensation time t _Kθ n _d to the desired degree of condensation. The resin solution is then cooled to room temperature in a condenser with the resin solution cooled to below 100 ^° C. after 20 seconds and to room temperature after 1 minute.

The characterization is carried out as described in Examples 1 to 3.

The parameters of the tubular reactor plant (reaction temperatures, reaction volumes, residence times) for the production of a special type of resin are determined as a function of the planned throughput in preliminary tests.

Comparative Example 1

Melamine, water, formalin solution and KOH are placed in the reactor with stirring at T _m (room temperature) and then heated to T _k 115 ⁰ C within about 25 minutes. After entering the clear point, the resin is still at 115 ⁰ C under autogenous pressure further condensed until it has a water compatibility of 0.3 after cooling. The characterization is carried out as described in Examples 1 to 3.

Comparative Example 2:

The experiment is carried out as described in Comparative Example 1, but with the change that the reaction takes place under reflux. After about 20 minutes, the state of the reflux is reached and the reaction is continued until the clear point. After reaching the

Klarpunktes the reaction solution is cooled. At this time, the resin solution has already condensed to such an extent that further condensation causes precipitation of the resin from the solution. The characterization is carried out as described in Examples 1 to 3.

It turns out that as a result of the separate heating of the reactants formalin and melamine, much more stable resin solutions are obtained. It can also be seen that increasing the mixing temperature T _m further increases the stability of the resin solutions.

Composite material and its production

With a melamine resin, e.g. As described above, the composite material according to the invention can be produced. As mentioned above, other resin materials may also be used.

FIG. 3 shows a first embodiment of the method. FIG. 3 shows a first embodiment of the co-kneader (co-kneader configuration 1). The kneading elements 100 are diamond-shaped in the drawing, black filled, the conveyor elements 101 shown oblong, parallelogram filled white. Not shown are the

Differential dosing scales for solid and / or liquid substances, as well as the high-pressure melt pump, the distributor and the tool.

The formulas for the composites

Kneader configuration 1 are shown in Table 4. The ingredients are premixed individually or partially premixed at the entry 20 into the feed screw via differential metering scales for solid and / or liquid substances, not shown here (for example, Brabender, K-Thron).

In a CoKneter MDK 46-D11 with 9 kneaders in 2 zones and an extended feed zone with 5 feed elements and then with a degassing and directly flanged high-pressure melt pump Maag Extrex® Ex56-5 HP E, a distributor and a plate tool (4.0 x 160 mm ) with 3 heating zones, the individual components are metered into the feed hopper 20 of the inlet screw with a total throughput of 30 kg / h. The apparatus parameters for the co-kneader configuration 1 experiments are shown in Table 6. The mixture is melted after the third kneading block at a jacket temperature T (sheath) and a screw temperature T (screw). In the CoKneter, the melt temperatures T1 / T2 / T3 / T4 / T5 / T6 are set. The melt pump is heated with T (melt pump). On the suction side of the melt pump there is a pressure of p (suction side). The distributor is operated at T (distributor). in the Tool adjusts itself a pressure of p (pressure side). The process has pressure fluctuations of +/- 5%. The tool is cured in the 3 heating zones at T10 / T11 / T12.

At a throughput of 30 kg / h, the residence time in the entire system is about 2.5 minutes.

The properties of the specimens milled out of the extruded composite panels are listed in Table 8.

A co-kneader known per se (i.e., for example, a single-shaft screw machine) has a kneading box, e.g. can be opened lengthwise. In this kneading housing a mixing and kneading screw is stored. The kneader housing has several (e.g., 3) rows of individually interchangeable kneading pins, the arrangement of which is governed by the geometry of the mixing and kneading screw.

For temperature control with a heat transfer medium, the kneading housing has at least one jacket through which the heat transfer medium can flow.

The mixing and kneading screw can be designed as a plug-in shaft. On a support shaft individually replaceable conveying, mixing and kneading elements are pushed and fixed radially and axially by means of a profile toothing. The

Stub shaft is formed at least partially tempered.

The temperature control can also take place via a heat transfer medium.

Basically, a CoKneter (for example, a BUSS Kneader) has the following functional units:

- inlet openings - Feeding and melting zone

- Mixing and homogenizing zone

- optional degassing zone

- Jet

In an advantageously usable CoKneter, the raw materials are continuously added to the kneader, volumetrically or gravitometrically via an intake aid. The throughput is not dependent on the speed of the worm shaft, but on the setting on the dosing device.

A throughput and material-related limitation is determined by the drive power of the motor and the maximum speed-dependent load of the kneader.

For a given throughput, overloading of the motor and the mixer gear by increasing the speed of the worm shaft can be avoided.

Another feature of an advantageous co-kneader is that no pressure build-up is required for the homogenization work. The local pressure build-up, which may be necessary for melting, is achieved by appropriate cross-sectional constrictions.

Furthermore, it is advantageous if the worm helix of the CoKneters does not have a continuous worm helix. For example, if the helix has three breaks, helical wings are created on the shaft. Simultaneously with a full revolution of the worm shaft, an axial stroke movement of the worm shaft takes place via a corresponding gear. FIG. 4 shows a further embodiment of the co-kneader (co-kneader configuration 2). The kneading elements 100 are diamond-shaped in the drawing, black filled, the conveyor elements 101 shown oblong, parallelogram filled white. Not shown are the

The formulations for the composites made with co-kneader configuration 2 are given in Table 5. The design of the co-kneader is basically identical, but has some different details. The ingredients are metered individually or partially premixed into the feed screw at the first entry 20 via differential metering scales for solid and / or liquid substances, not shown here (for example, Brabender, K-Thron). Via an optional second entry 21, e.g. Water are added.

In a CoKneter MDK 46-D11 with 5 kneading elements in 2 zones and an extended feed zone with 9 conveying elements and then with a degassing and directly flanged high-pressure melt pump Maag Extrex® Ex56-5 HP E, a distributor and a plate tool (4.0 x 160 mm ) with 3 heating zones, the individual components are metered into the feed hopper 20 of the inlet screw with a total throughput of 30 kg / h. The apparatus parameters for the co-kneader configuration 2 experiments are shown in Table 7. The mixture is after the first

Kneading block melted at a jacket temperature T (sheath) and a screw temperature T (screw). In the CoKneter, the melt temperatures T7 / T8 / T9 are set. The Melting pump is heated with T (melt pump). On the suction side of the melt pump there is a pressure of p (suction side). The distributor is operated at T (distributor). The tool adjusts itself to a pressure of p (pressure side). The process has pressure fluctuations of +/- 5%. The tool is cured in the 3 heating zones at T10 / T11 / T12.

feedstocks

Resins (+ hardener systems)

Hipe®esin MPER4T5: etherified, modified melamine-formaldehyde resin, molar ratio of formaldehyde / melamine = 4, etherification 80%, Mw 6000 g / mol, viscosity 20 Pas at 130 ⁰ C, glass transition temperature Tg 42 ⁰ C, flakes. Hardener for Hipe®esin MPER4T5: guanidine sulfamate 50% / triisopropanolamine 50% (GS / TIPA)

Hipe®esin MF1.3T15: unetherified, modified melamine-formaldehyde resin, molar ratio of formaldehyde / melamine = 1.3, Mw 250 g / mol, viscosity 800 Pas at 100 ⁰ C, glass transition temperature Tg 52 ⁰ C, flakes.

Hipe®esin MF139T5: unetherified, modified melamine-formaldehyde resin, molar ratio formaldehyde / melamine = 1.6, Mw 250 g / mol, glass transition temperature Tg 65 ⁰ C, powder.

HipeΘesin Xilocolla S30M: urea-formaldehyde resin (UF resin), molar ratio formaldehyde / urea = 1.58, Mn 550 g / mol, glass transition temperature Tg 62 ⁰ C, powder. Hipe®esin Xilolam SlOO: melamine-urea-formaldehyde resin (MUF resin), molar ratio formaldehyde / (melamine + urea) = 1.8, Mn 350 g / mol, glass transition temperature Tg 66 ⁰ C, powder.

Novolak EXP E069: phenol-formaldehyde resin, molar ratio of formaldehyde / phenol = 0.8, Mw 5000 g / mol, glass transition temperature Tg 40 ⁰ C, pH 6.4, viscosity 240 Pas at 110 ⁰ C, powder, colorless. Hardener for Novolak EXP E069: Hexamethylenetetramine HMTA

Epoxy resin: based on bisphenol A diglycidyl ether, Mw 3600 g / mol, viscosity 35 Pas at 130 ⁰ C, glass transition point Tg 80 ⁰ C, powder. Hardener for the epoxy resin: dicyandiamide DCDA

HipeΘesin MPER5-H: hydroxyethyl methacrylate (HEMA) - modified, etherified melamine-formaldehyde resin, HEMA equivalent content 50%, Mw 20000 g / mol, molar ratio formaldehyde / melamine = 5, residual HEMA content approx. 5%, viscosity 11 Pas at 100 ⁰ C, flakes. Hardener for Hipe®esin MPER5-H: dicumyl peroxide DCP.

UP resin: unsaturated polyester resin, maleic anhydride ratio MSA / isophthalic acid IPA / propylene glycol PG / diethylene glycol DEG = 1: 1.15: 1.14: 1.44, acid number 18 mgKOH / g, hydroxy number 22.5 mgKOH / g, Mn 2750 g / mol, styrene content 10%, Viscosity 4 Pas at 80 ^° C. Hardener for the unsaturated polyester resin: dicumyl peroxide DCP.

wood materials

Lignocel BK40-90: Wood fibers, approx. 50% cellulose, approx. 25% hemicellulose, approx. 25% lignin, moisture 2-4%, fiber length (average) 0.5 mm. Werzalith F / N: F ... fine chipboard, N ... standard chipboard, wood, natural, about 60% beech, 30% spruce, 10% poplar, humidity 2-4%, fine chip: fiber length (average) 0.25 mm, Standard chip: fiber length (mean value) 0.8 mm.

Fillers / reinforcements

Arbocel: cellulose fibers, fiber length (average) 0.5 mm.

Microsoil 40: calcium carbonate, fine powder.

Talc: Magnesium oxide-silica phyllosilicate, fine powder.

Sipernat 2200: silicic acid based on aluminum and calcium silicates, hydrophilic, particle size 300 microns, pH (5% suspension in water) 6, powder.

Sipernat D17: silicic acid based on aluminum and calcium silicates, hydrophobic, pH (5% suspension in water) 8, powder.

GF 3540: glass fiber, short fiber 4.5 mm, aluminum borosilicate glass, aminosilane size.

additives

Naftosafe PHX 369 D: Polymer additive (flow aid, stabilizer) based on stearates, PE waxes, oxidized waxes, lead-free, neutral.

Capa 6400: polycaprolactone (linear polyester), Mw 37000, melting point 60 ^° C., viscosity 190 Pas at 130 ^° C.

Mowital B30T: polyvinyl butyral, Mw 35000, contents [% by weight] of polyvinyl alcohol 24-27 / polyvinyl acetate 1-4 / polyvinyl butyral 69-75, glass transition temperature Tg 70 ⁰ C, viscosity 1500 Pas at 150 ⁰ C.

Vinnapas UW4FS: 100% polyvinyl acetate, glass transition temperature Tg of 44 ⁰ C, Mw 270,000, viscosity 40,000 Pas (oscillation 0.1 Hz) at 130 ⁰ C.

PEG 35000: polyethylene glycol, Mw 35000, melting point 65 ^° C.

Further embodiments

In a further embodiment, the resin material can be produced as follows:

a) A mixture of melamine, formaldehyde and water which is under excess pressure and has a pH greater than 7 is prepared,

b) where melamine and formaldehyde are heated separately and then

c) are mixed together and wherein during mixing a mixing temperature T _m of greater than 100 ⁰ C is present, then

d) the reaction is conducted at the mixing temperature T _m until reaching the clear point, then

e) is further condensed at the condensation temperature T _k until reaching the desired water compatibility. Advantageously, after step e) is cooled to room temperature and the resin solution is discharged.

The reactants are heated separately, so that there is already an elevated temperature during the mixing of the reactants.

The mixing temperature T _m is understood to be the temperature which occurs when melamine, formaldehyde and water are mixed.

The condensation temperature T _k is the temperature at which, after reaching the clear point, the resin condensation is continued until the desired water compatibility is achieved.

Advantageously, melamine-formaldehyde resin solution (stable MF resin solution) having a F / M ratio ≤ 1.5 is dissolved, which at 20 ° C has a water compatibility of 0.15 to 4.0 and at F / M 1.0 a Stability of at least 5 h, with F / M 1.1 one

Stability of at least 6 h, stability of at least 13 h in the case of F / M 1.2, stability of at least 24 h in the case of F / M 1.3, stability of at least 50 h in the case of F / M 1.4 and stability of at least 50 h in the case of F / M 1.4 / M 1.5 has a stability of at least 200 h, within the range limits 1.0 <F / M <

1.1, 1.1 <F / M <1.2, 1.2 <F / M <1.3, 1.3 <F / M <1.4, 1.4 <F / M <1, 5, the stability of the resin solution has a linear dependence between the stabilities of the respective F / M range limits.

It is advantageous if the ratio

VI = (total amounts of melamine and monomers) / (Sum amounts of dimers, trimers and oligomers)

between 1.1 and 1.7.

The resin solutions are characterized by a very good storage stability and ease of manufacture. The resin solutions have neither very highly condensed portions nor excessive levels of unreacted melamine. Due to this chemical uniformity they show a storage stability, which is from at least 5 h up to over 250 h.

Particularly preferred are such melamine

Formaldehyde resin solutions in which Vl is between 1.2 and 1.5 and / or which is a ratio

V2 = (content of monomers) / (sum amounts of dimers, trimers and oligomers) between 0.8 and 1.4, in particular between 0.85 and 1.25.

Melamine-formaldehyde resin solutions with these properties have particularly high stabilities, which are up to> 250 h, on.

Particularly preferred are those melamine-formaldehyde resin solutions which have a formaldehyde / melamine ratio of 1.0 to 1.5, particularly preferably 1.1 to 1.4. These resins have sufficiently low levels of formaldehyde with good stability and manufacturing properties. Generally, as the F / M ratio increases, the stabilities of the resin solutions increase.

It is furthermore advantageous if the mixture has a pH of between 7 and 14, in particular between 7.5 and 12. For pH adjustment, common inorganic and organic bases such as KOH, NaOH, Ca (OH) ₂ , amines and alkanolamines can be used.

In the preparation of the liquid mixture, it is advantageous that the three reactants melamine, formaldehyde and water are heated separately. It is also possible to heat melamine and water together, but separately from formaldehyde and / or formaldehyde and water together, but separately from melamine. It is also possible to co-heat the melamine with a portion of the water and co-heat the formaldehyde with a portion of the water.

It is particularly preferred if the melamine are heated separately as an aqueous suspension or aqueous solution and the aqueous formaldehyde to T _m greater than 100 ⁰ C and then the formaldehyde solution and a base for pH adjustment under pressure of the well-stirred melamine suspension or Solution are added.

In this way, the reaction is started at the mixing temperature T _m with a defined start and continued at T _m to the clear point.

In contrast, when heating up a common

Mixing of all reactants by apparatus parameters affects the heating rate, resulting in different reaction times, reaction conditions and nonuniform Resin properties leads. This also contributes to the fact that the heating rate is slow.

By contrast, in embodiments of the resins, by eliminating the heating time of a common mixture of the reactants, the reaction can be carried out in a reproducible and defined manner, resulting in more uniform resin solutions.

Preferably, the formaldehyde is used as an aqueous solution with a formaldehyde content greater than 36 wt.%.

A higher concentration of the formaldehyde is positive, since in this case the melamine more water for suspension formation is available and thus the stirrability of the suspension, the distribution of melamine and its dissolution process is improved.

In general, any desired source of formaldehyde, for example methanol-stabilized, melamine-stabilized, unstabilized or else para-formaldehyde can be used.

It is advantageous if the mixing temperature T _m between 100 and 200 ⁰ C, more preferably between 110 and 150 ⁰ C. The higher the mixing temperature T _m , the better the melamine solubility and thus the availability of the melamine for the reaction with the formaldehyde. The higher T _m , the more uniform the resulting resin solution.

The pressure prevailing in the reaction corresponds to the boiling pressure of the liquid mixture at the prevailing temperature. According to a temperature T _m between 100 and 200 ⁰ C, the overpressure is up to about 10 bar overpressure. It is preferred if the mixing temperature T _m and the condensation temperature T _{k are the} same. This offers the advantage that the reaction is very simple and yet high-quality and stable resin solutions are available.

But it is also possible that after reaching the clear point, the temperature is lowered and is further condensed at the lower temperature to the desired water compatibility. The concept of

Water compatibility will be explained in more detail below in connection with an exemplary embodiment.

In this case, the condensation temperature T _{k is} less than the mixing temperature T _m . Cooling from T _m to T _k can be both fast and slow. For a lower condensation temperature suggests that the condensation is slower and thus the desired water compatibility can be very well adjusted.

The melamine-formaldehyde resin solution preferably has a solids content of from 20 to 80% by weight, particularly preferably from 40 to 70% by weight. Melamine-formaldehyde resin solutions with these solids contents can be stored and processed particularly well.

It is preferred if the melamine-formaldehyde resin solution has a water compatibility of 0.2 to 1.5, in particular that the condensation is carried out to a water compatibility of 0.4 to 1.5. It is particularly advantageous if the water compatibility is 0.2 to 1, in particular that the condensation is carried out to a water compatibility of 0.5 to 1.

In these areas of water compatibility, the resin solutions have maximum stability.

The storage stability of the resin solutions is at least 5 h. Particularly advantageous are those resin solutions whose storage stability is at least 24 h. These resin solutions, and especially those with more than 40 hours storage stability, provide a very good time buffer between the resin synthesis and the further processing of the resin solution.

It is advantageous if the melamine-formaldehyde resin solution is spray-dried. Thus, the same processing capabilities as the standard melamine-formaldehyde resins are given with higher formaldehyde content and the possible storage time of the resin powder is generally many times higher than that of the resin solutions.

In one embodiment, the composite is made with a resin wherein a mixture of melamine, formaldehyde, and water which is under overpressure and has a pH greater than 7 is prepared, wherein melamine and formaldehyde are heated separately and then mixed together and wherein during mixing a mixing temperature T _m of greater than 100 ⁰ C is present, then a) the reaction at the mixing temperature T _{m is performed} until reaching the clear point, then b) at the condensation temperature T _k until

After reaching the desired water compatibility is further condensed, whereupon cooled to room temperature and the resin solution is discharged.

Advantageously, the process is carried out batchwise, wherein a stirred tank is used as the reaction apparatus.

During the cooling from the condensation temperature T _k to below 100 ⁰ C, appreciable postcondensation still occurs. The required condensation time at T _k , taking into account the postcondensation to the desired water compatibility can be easily determined from preliminary tests. It is also possible during the reaction to follow the condensation progress by sampling and determination of the water compatibility and to control the reaction with it.

For more detailed characterization of the resin solutions, for example gel permeation chromatography (GPC) and liquid chromatography with mass and / or UV detector (HPLC-MS, HPLC-UV) can be used.

The preparation of a melamine-formaldehyde resin solution can also be carried out so that a mixture of melamine, formaldehyde and water, which has a pH greater than 7, is reacted at a reaction temperature Tr> 100 ⁰ C, wherein after the presence of the mixture the reaction temperature T _{r is reached} in less than 5 minutes, the reaction is carried out until reaching the clear point, then at the condensation temperature T _k until reaching the desired Water compatibility is further condensed, whereupon cooled to room temperature and the resin solution is discharged.

The pH is preferably 7 to 14, more preferably 7.5 to 12.

The solids content of the resin solution is preferably 20 to 80% by weight, particularly preferably 40 to 70% by weight.

It is possible to heat melamine and / or formaldehyde and / or water separately from each other and then mix together. The separate heating can take place up to the reaction temperature Tr. In this case, the reaction temperature T _r corresponds to the mixing temperature T _m . The process in this case is preferably carried out batchwise in a stirred tank.

The separate heating can also be carried out below the reaction temperature T _r . In this case, the mixing temperature T _{m is} below the reaction temperature T _r and further heating to the reaction temperature T _r takes less than 5 minutes.

In this case, or if the reactants are not heated separately but first mixed and then brought to T _r in less than 5 minutes, the process is preferably carried out continuously in a tubular reactor.

The tubular reactor can be constructed from one or more, interconnected containers. Preferably, the temperature profile for adjusting the desired temperatures T _m , T _r , T _{k is set} in the tubular reactor by separate over the reactor length arranged heating circuits. The residence time distribution in the tubular reactor is between ideal plug flow and laminar flow. The throughput in the tubular reactor depends on the required residence time at a defined reactor geometry, which is necessary in order to achieve the desired properties of the final product can.

In principle, the method is also suitable for producing already known melamine-formaldehyde resin solutions having a formaldehyde / melamine ratio of greater than 1.5.

The melamine-formaldehyde resin solution may e.g. be used for the production of laminates, composites, molding compounds or compounds.

Non-crosslinked thermoplastics, lubricants or other additives such as flame retardants, pigments, stabilizers, catalysts, UV absorbers and / or free-radical scavengers as such or mixtures thereof can advantageously be used as additives for the composites. It is advantageous if the additive used is a mixture of uncrosslinked thermoplastic and lubricant in a proportion of not more than 5% by weight of lubricant and a proportion of uncrosslinked thermoplastic of not more than 10% by weight, based in each case on the mixed materials.

Advantageous lubricants are hydrocarbon waxes, oxidized hydrocarbon waxes, zinc stearate, Calcium stearate, magnesium stearate or other metal soaps and / or mixtures of these.

In another method, the components of the composite are combined in a worm shaft device with at least one kneading agent and at least one mixing agent.

It is particularly advantageous if the worm shaft device has at least one co-kneader. The known working principle of a co-kneader is based on the fact that the material to be extruded is subjected to a combined rotary / lifting movement. Within the mixing and kneading section (i.e., inside the kneader housing), this combined movement is e.g. transmitted by means of Schneckenflügeln the mixing and kneading screw on the material to be extruded.

In this procedure, the material to be extruded is compacted, plasticized and homogenized, primarily by frictional heat. By a product-tuned temperature of the kneader housing and / or the mixing and kneading screw, the operation can be influenced. Further details will be explained in connection with the exemplary embodiments.

The person skilled in the art recognizes that individual method steps or details of the method steps in the exemplary embodiments illustrated can be combined with one another. LIST OF REFERENCE NUMBERS

1 formaldehyde charge

2 preheaters 3 valves

4 Charging melamine, water, lye

5 lye dosing tanks

6 stirred tank

7 discharge melamine formaldehyde resin solution

11 Charging melamine, formaldehyde, water, lye

12 suspension containers

13 dosing pump

14 tubular reactor 15 coolers

16 relaxation valve

17 discharge melamine-formaldehyde resin solution

20 entry 21 entry

Table 2: Examples 4 and 5

Table 3: Comparative Examples 1 and 2

The resin solutions can be prepared simply and reproducibly and have significantly better stabilities than the comparative examples from the literature.

Table 5: Feedstocks for examples with co-kneader configuration 2

00

Table 6: Apparatus parameters for examples with co-kneader configuration 1

Table 7: Apparatus parameters for examples with co-kneader configuration 2

Claims

claims

1. Composite material

producible by

a) the mixture of at least one resin material with at least one second material,

b) subjecting the blended materials in a kneader to combined rotary and reciprocating motion and reflow,

c) a subsequent compression of the mixed and melted materials and a

d) feeding to a forming tool and subsequent hardening.

2. Composite material according to claim 1, characterized in that the at least one second material has a proportion of 20 to 85 wt .-% of the mass of the mixed materials.

3. A composite material according to claim 1 or 2, characterized in that the at least one second material has a content of 30 to 80 wt .-%, in particular a proportion of 50 to 75 wt .-% of the mass of the mixed materials.

4. Composite material according to at least one of the preceding claims, characterized in that the second material at least a proportion of wood, a proportion cellulose, a proportion of an inorganic filler, a proportion of a cellulose derivative, a content of acteylated cellulose, hemicellulose, lignin, lignin derivatives and / or a proportion of modified cellulose.

5. Composite material according to claim 4, characterized in that the proportion of wood in the form of wood flour, wood particles, wood granules, wood fibers and / or wood chips is present.

6. A composite material according to at least one of the preceding claims, characterized by a proportion of additives from 0 to 30 wt .-% of the mass of the mixed materials.

7. A composite material according to claim 6, characterized in that as additives at least one uncrosslinked thermoplastic, at least one lubricant, polyvinyl butyral - polyvinyl acetate - polyvinyl alcohol, at least one polyol, at least one flame retardant, at least one pigment, at least one stabilizer, at least one polyether polyol, at least one Polyester polyol, at least one catalyst, at least one UV absorber and / or at least one radical scavenger are used as such or mixtures thereof.

8. A composite material according to claim 6 or 7, characterized in that the additive is a mixture of uncrosslinked thermoplastic and lubricant in a proportion of not more than 5 wt .-% lubricant and a proportion of uncrosslinked thermoplastic of not more than 10 wt .-%, each based on the mixed materials is used.

9. A composite material according to at least one of claims 6 to 8, characterized in that as a lubricant at least one hydrocarbon wax, at least one oxidized hydrocarbon wax, at least one

Zinc stearate, at least one calcium stearate, at least one magnesium stearate or other metal soaps and / or mixtures of these substances are used.

10. Composite material according to at least one of the preceding claims, characterized in that during the compression of the materials, a pressure of less than 1000 bar is applied.

11. A composite material according to at least one of the preceding claims, characterized in that the sliding properties of the mixed and molten materials are such that the pressure difference between the compression and the shaping is less than 1000 bar, in particular less than 500 bar.

12. A composite material according to at least one of the preceding claims, characterized in that the at least one resin material has a proportion of 15 to 60 wt .-% of the mixed materials.

13. The composite material according to at least one of the preceding claims, characterized in that the at least one resin material has a proportion of 20 to 40 wt .-% of the mixed materials.

14. Composite material according to at least one of the preceding claims, characterized in that the Resin material at least a proportion of a resin, a proportion of a resin solution, a proportion of a resin emulsion, a proportion of a resin dispersion and / or a proportion of a resin melt.

15. A composite material according to at least one of the preceding claims, characterized in that the at least one resin material has at least one Aminoplastbildner.

16. Composite material according to claim 15, characterized in that the at least one

Aminoplastharzbildner melamine, urea, dicyandiamide, guanamines, guanidine, guanidine derivatives, biguanide, biguanide derivatives, substituted melamines and / or substituted ureas.

17. A composite material according to at least one of the preceding claims, characterized by at least one resin material based on urea, guanidine,

Aminoplasts, triazine, acrylic, phenol, polyester, melamine, epoxide, alkyd, a lignin polymer, as well as mixtures of these substances.

18. Composite material according to at least one of the preceding claims, characterized by at least one resin material based on melamine and / or urea.

19. A composite material according to at least one of the preceding claims, characterized by at least one resin material based on a melamine and / or urea-formaldehyde resin.

20. A composite material according to at least one of the preceding claims, characterized in that at least one melamine and / or urea-formaldehyde resin is an etherified resin and / or a partially etherified resin and / or an unetherified resin.

21. A composite material according to at least one of the preceding claims, characterized in that at least one resin is a modified, unetherified melamine and / or urea-formaldehyde resin or an unmodified unetherified melamine and / or urea-formaldehyde resin.

22. Composite material according to at least one of the preceding claims, characterized in that at least one resin is an unmodified, unetherified melamine and / or urea-formaldehyde resin which can be prepared with a molar ratio of formaldehyde to amino component of less than or equal to 1.5.

23. A composite material according to at least one of the preceding claims, characterized in that it is present as a plate, profile or tube.

24. Use of composite materials according to at least one of claims 1 to 23 in windows, doors, trim elements and roof elements in the outdoor area, and in the sports and leisure sector for garden furniture, outdoor seating and playground design.

25. A method for producing a composite material, characterized in that a) at least one resin material is mixed with at least one second material,

b) wherein the mixed materials in a kneader a combined rotary and lifting movement and a

Be subjected to melting,

c) then the mixed and melted materials are compressed and

d) fed to a shaping tool and cured.

26. The method according to claim 25, characterized in that the mixing and melting takes place in a screw shaft device, in particular with at least one CoKneter.

27. The method according to claim 25 or 26, characterized in that the screw shaft device performs a direct extrusion.

28. The method according to at least one of claims 25 to 27, characterized in that the molten material is conveyed by at least one pumping device by a profile tool.

29. The method according to claim 28, characterized in that the pumping device has at least one gear pump, at least one single-screw extruder and / or at least one twin-screw extruder.

30. The method according to at least one of claims 25 to 29, characterized in that the dosage of at least one the components in the screw shaft device in the form of individual components or in the form of a produced free-flowing mixture of the individual components takes place.

31. The method according to at least one of claims 25 to 30, characterized in that the component mixtures or individual components are conveyed via an inlet screw into the CoKneter, in the kneading means and / or the mixing means.

32. The method according to at least one of claims 25 to 31, characterized in that wood, the resin material, in particular melamine resins and / or the additives in the at least one kneading agent, the at least one mixing agent and / or the at least one CoKneter melted homogenized , and degassed and the mixture is then conveyed to a melt pump.

33. The method according to at least one of claims 25 to 32, characterized in that a melting process for the

Components by rotation speeds of the kneading agent and / or the mixing agent of 80 U / min to 200 U / min is started.

34. The method according to at least one of claims 25 to 34, characterized in that for starting the temperatures of

Co kneader screw from 20 ⁰ C to 100 ⁰ C and the temperatures of CoKnetermanteltempierzonen be set from 60 ⁰ C to 160 ⁰ C.

35. The method according to at least one of claims 25 to 34, characterized in that the melt pump is flanged via a transition piece to the CoKneteraustrag.

36. The method according to claim 35, characterized in that a starting opening is integrated in the transition piece.

37. The method according to at least one of claims 25 to 36, characterized in that the high-pressure melt pump the

Pressure build-up of 50 to 1000 bar brings to the profile tool.

38. The method according to at least one of claims 25 to 37,

characterized in that

a) the wood, melamine resins and additives in CoKnetermanteltempierzonen of about 60 to 160 ⁰ C and screw temperatures of 20 to 100 ⁰ C are melted, homogenized and degassed,

b) the mixture at a mass temperature of about 80 ⁰ C to 200 ° C is compressed,

c) is then introduced with elevation of temperature to 110 to 300 ⁰ C in a forming tool, in which the crosslinking takes place, and

d) the finished composite material is discharged.