DE2617357A1 - METHOD FOR MANUFACTURING A COMPOSITE BODY AND COMPOSITE BODY MANUFACTURED AFTER THAT - Google Patents

Description

PATENT ADVOCATE

DIFL-JN3. WALTER GEIERSBACH

D ~ 4 DOSSELDORFll
WICKRATHER SiRAiSE 43, TEUFON: (0211) 5J2234

Process for the production of a composite body and composite bodies produced thereafter

The present invention relates to a method of manufacture a composite body made of a molded body made of polyurethane and one made of another plastic, wherein the reactant mixture forming the polyurethane molding before its complete reaction with the plastic molding

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ORfGlNAL INSPECTED

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is brought into contact, as well as one prepared according to this method Composite body.

The connection of polyurethane with other plastics often poses a problem in practice. There are already a large number of proposed solutions for eliminating this problem, but mostly only for very specific combinations and possible uses are viable.

So it is known, for example, to be connected with the polyurethane Oxidative plastic surface, e.g. by glow discharge in a vacuum, corana discharge with normal, medium or high frequency, or by attacking strongly oxidizing acids or exposure to oxidizing flames. These methods have one hand the disadvantage that they are expensive in terms of equipment, but on the other hand they may bring about more profound changes in properties at the treated area, which as a rule have an adverse effect on the properties. Also is that These individual methods can only be used for certain plastic classes, so that different ones are used more frequently Plastics always the treatment method must be changed.

It is also known the thermoplastic properties of polyurethane by adding thermoplastic components to the reaction mixture of the starting components forming the polyurethane. Through this the polyurethane can be improved in terms of its behavior during flame lamination. Apart from the fact that the method of flame lamination requires some effort from the device side, this method is restricted to certain plastics whose surface is too the polyurethane decomposition products is sufficiently affine, with the disadvantage that if the polyurethane in In the form of a foam, the pores when ———

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Flame lamination can be closed, creating the most desired Air permeability is reduced.

It is also known in the production of bitumen paper-laminated Polyurethane foams the bitumen paper with opposite isocyanates to impregnate reactive compounds, plasticizers or tackifiers. As isocyanate-reactive compounds For the purposes of this known method, hydroxyl-containing compounds or amines are suitable. Come as a plasticizer various phthalates, sulfonates and phosphates are possible according to this method. Natural resins, such as rosin, are used as tackifiers, however also synthetic resins such as melamine resins or phenolic resins. All of these substances can either be on the bituminous material can be applied in bulk or in solution, or incorporated directly into the bitumen.

When using isocyanate-reactive compounds according to this known process, one uses apparently the colloidal nature of the bitumen _/ which enables a solution or emulsification of the compound in question in the liquid phase, whereas the solid phase consisting of polycyclic hydrocarbons with an average molecular weight of about one hundred thousand is not suitable for the physical or chemical bonding of such polar compounds. When applying a polyurethane-forming reaction mixture, the isocyanate, which has a relatively high vapor pressure, can react with the reactive compound distributed in the liquid phase of the bitumen and create a deep bond between the biturainic material and the polyurethane foam.

In addition, the materials that have been impregnated with bitumen, e.g. paper, textiles or the like., a certain absorbency that «Ie for the absorption of the applied to the bituminous material or isocyanate-reactive, incorporated into the bitumen

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Connections enabled. This naturally favors the adhesion extraordinary, since the isocycnate is now applied to the polyurethane-forming components Mixing on the bituminized material partially even in this, d. H. in the paper and in the textiles ^ is bound "

The mode of action of the plasticizers that can also be used to improve adhesion according to this known method cannot be explained in this way. but is apparently only to be seen in connection with bitumen, do such plasticizers, e.g. phthalic acid esters, phosphoric acid esters, aminocarboxylic acid esters, etc., if they are used to soften, for example Polyvinyl chloride are used, in terms of the adhesiveness dos polyvinyl chloride compared to polyurethane rather the opposite, ie cause a deterioration in liability.

D; th present invention has set itself the goal of a detention method to create between molded bodies made of polyurethane and another plastic that are generally used for every plastic can without the need for special, complicated devices.

This is inventively achieved in that the plastic molded body, or the constituent plastic impregnated at least in the connecting it to the polyurethane molding to the surface portion with a respect to at least one component of Reaktantengenisches reactive agent, or is added. In this way, a reactive layer is produced on the surface of the plastic molding, the adhesive behavior of which is excellent in statu nascendi with respect to polyurethane. Based on the known state of the art, which uses bituminized materials, this behavior was quite surprising for the person skilled in the art, since the liquid phase present in bitumen is completely absent in plastics and one had to assume that the Van der V / aal forces between the essentially as hydrophobic to be designated plastics and the

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used, much more polar compounds acting as adhesion promoters would not be large enough to produce a to maintain good adhesion. * '

The second possible effect with bituminized materials, namely the penetration of the reactive agent into the base material / is excluded with a fully plastic body, so that also from from this point of view, the considerations of the person skilled in the art did not give the method proposed according to the invention any chances.

In addition, it was feared that the physical properties, in particular the gas permeability and the aging behavior of the plastics at the junction with the polyurethane, would be negatively affected, so that even with good adhesion, the area would become brittle the connection point calculated, which naturally plays no role with bitumen due to the liquid, mobile phase.

The method according to the invention has particular advantages when the reactive agent has functional groups which are Η-active, e.g. -OH, -SH, ΝΗ, -Ν ^, - ΟΗ. It can then be the inventive Due to the stability of these groups, the method can be carried out within relatively long periods of time, as the storage life of the impregnated Plastic molded body is almost unlimited.

If an agent is used that has functional groups that react with active H atoms, e.g. -NCO, -NCS, so can you can thereby achieve a particularly intensive connection, even if the concentrations used are only relatively low.

In order to take into account the possibility that a plastic

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Provided molded body of different dimensions can be connected with polyurethane at different points, it is expedient if the reactive agent is evenly distributed in the plastic. This can be achieved in two ways: either the reactive agent is added to the plastic during its manufacture, or it is added to the plastic during its further processing. In the former case, the agent is incorporated into the plastic, for example already during its polymerization. Naturally, this leads to a particularly intense connection. This method also has the advantage that the company processing the plastic does not have to incorporate any additional steps into its procedure. The second option again has the advantage over the aforementioned option that, if necessary, different agents can be used for different purposes, the dosage of which can be varied accordingly. Here, too, the technology used so far does not have to be changed, since mixing in a substance on a rolling mill, an internal mixer or an extruder does not require any additional measures.

Favorable adhesion properties are achieved in a plastic molded body,

in which the reactive agent is evenly distributed, is achieved when about 3 to about 30% by weight , preferably about 5 to about 15% by weight, of reactive agent are added to the plastic Agents such as triethanolamine, glycerine, pentaerythritol, only inadequate adhesion can be achieved.

The influence on the properties of the plastic molded body is greater than about 30% by weight already too big, so that despite good adhesion such

Composite bodies no longer have satisfactory properties. In general, good results are obtained when about 5

until about 15 Cev »% of the reactive agent is added to the plastic ·

One even greater variability in terms of the type of used reactive agent, as well as its concentration is possible if it is im

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In the course of the production of the plastic molding on the relevant Surface part is applied. In addition to the advantage of being economical, this method has "another advantage," which is that Due to the pressure that usually occurs during the production of a molding, the adhesion is the same over the entire desired surface is · At the same time it is achieved that the properties of the plastic molding itself are not changed in any way ·

A particularly advantageous method for producing one according to the invention impregnated polyvinyl chloride film consists in that on a possibly reinforcing insert made of a woven, knitted fabric, fleece or the like. Made of textile, plastic or metal fibers, produced by painting or dipping from a polyvinyl chloride paste, ungelated polyvinyl chloride film by means of a roller or the like evenly applied thin film of the reactive agent, the polyvinyl chloride film gelled and then, optionally after cooling with the polyurethane-forming reactant mixture, preferably continuously, is coated in particular according to the method of DT-AS 1,247,612. This process allows the production of composite bodies between polyvinyl chloride films and polyurethane moldings, whereby the application of the reactive agent to the still ungelled Polyvinyl chloride film a particularly intimate connection is achieved. In addition, this process can be used without problems for the production processes customary today for polyvinyl chloride films.

s — reactive agent on — the relevant surface of the finished Applied plastic molding, it is possible for every final producer to use the invention without any special precautions To apply procedures and to take advantage of their beneficial effects

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There is particularly good adhesion if the upper

Area of the plastic molded body about 5 to 100 g / m, preferably

about 10 to about 30 g / m of reactive agent is applied. Below about 5 g, as already stated above, the concentration is too low, properties, e.g. gas permeability, are more than about 100 g already too effective. In addition, at amounts above about 100 g / m 2 of the reactive agent, the economics of the process are lower no longer given. Good adhesion is generally achieved when about 10 to 30 g / m 2 of the reactive agent is applied.

It is particularly advantageous if the reactive agent is multifunctional, preferably trifunctional, and has a molecular weight of less than about 500, preferably less than about 300. As a result, an optimal effect can be achieved even with relatively small amounts of the agent applied, since the local concentration of reactive centers is nevertheless high. As a result, the physical properties of the plastic and also of the polyurethane at the connection point are only slightly influenced, which is beneficial in any case.

This is of particular importance when, for example, a polyvinyl chloride film is provided with a rigid polyurethane foam and the resulting composite body, e.g. as a roofing element is used, to be connected to a second similar element, in such a way that the PVC film of the element Protrudes beyond the edge of the rigid polyurethane foam, which

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protruding part is to be connected to the PVC film of the adjacent element. +

The connection of PVC foils to one another can be done by welding be achieved. In addition to hot gas welding and heating element welding, a welding process commonly used for this purpose is a

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A heated wedge is guided between the surfaces to be welded, the solvent welding process. This is a welding process whereby the areas to be welded are swollen by a solvent and then pressed together. Since this method of welding thermoplastics, especially PVC, is very common is used, the guarantee must be given that the plastic, especially the polyvinyl chloride, even after its impregnation can be welded to the reactive agent in this way. It However, it has been shown that when using relatively high molecular weight compounds for the purpose according to the invention, e.g. of polyols,

As they are usually used for polyurethane production, the surface of the plastic, in particular a PVC film, is changed in such a way that swelling does not take place to a sufficient extent within a reasonable time. However, if the reactive agent used is a compound that has a relatively low molecular weight and is at least trifunctional at the same time, e.g. triethanolamine, diethylenetriamine, pentaethylene tetramine (1,2,6) -hexanetriol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, 2,3, - Dimercaptopropanol-1, tetraethylene petamine N, N, N ¹ , N '- (hydroxypropyl) -ethylene-diamine and many others.

The method according to the invention can be used with particular advantage Use plastic moldings made of a thermoplastic, e.g. Polyvinyl chloride, polyethylene, polypropylene, polystyrene or the like.

A particularly useful application of the method according to the invention leads to a composite body which, as a sandwich element with a rigid polyurethane foam core and at least one outer skin made of plastic, e.g. polyvinyl chloride, polyethylene, polypropylene, polyester, ethylene-propylene rubber or the like. Such composite bodies are suitable as insulating elements, which due to the plastic coating without additional protective cover, e.g. for covering

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Flat roofs, can be used. It is used in this case Upper lamination material as roof cladding · An aluminum foil is particularly suitable as the lower lamination material, which has the function of Vapor barrier takes over "

It is particularly favorable for such a purpose when the plastic impregnated with the reactive agent has water vapor permeability of at least 4 g / m according to DIN 53.122. In this case it is guaranteed that otherwise possibly Water vapor condensing in the joint between two composite bodies used as roof elements through the plastic to the outside air can diffuse. In addition, it has been shown that plastics whose structure has such a minimum water vapor permeability allowed to be impregnated particularly sparingly with the reactive agent and still have excellent adhesion with the polyurethane give·

The required water vapor permeability can be achieved in particular if the plastic skin is covered with a woven fabric, knitted fabric, Fleece made of textile, plastic or metal threads is strengthened. The points of contact between fabric and plastic, as well as the fabric even as a result of its suction, promote water vapor permeability in this case.

In this regard, optimal conditions can be achieved if the reactive agent used as an impregnating agent is also incorporated into the polyurethane as a crosslinking agent. This does not only apply to foamed products Polyurethane, but also for compact polyurethane elastomer. The similarity of that in the polyurethane and at the junction Agents present with the plastic molding not only lead to a particularly firm, but also a particularly homogeneous connection, i.e. that the connection point reflects the properties of the

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Composite body practically not influenced at all, but its properties only on the one hand by the plastic molded body and on the other hand are determined by polyurethane.

When using a composite body according to the invention as a roof element, it is expedient if the plastic skin partially projects beyond the edge of the rigid polyurethane foam body so that an adjacent composite body of the same type is overlapped. The overlapping part of the plastic skin can then be connected to the plastic skin of the adjacent element. This connection can be made by gluing, preferably by welding. A welded connection is preferable because it will last longer. As already mentioned above, it is important for the weldability of the plastic skin that there is not an excessive amount of reactive agent in the plastic, since otherwise the swellability is too greatly reduced. Therefore, in this case, an agent must be used which is extremely reactive and can therefore be applied in a correspondingly low concentration. Triethanolamine, glycerine, N, N, N ¹ , N '- (hydroxypropyl) ethylenediamine etc. are suitable for this purpose.

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The invention is explained in more detail below with the aid of examples:

1 · Reactive agent polymerized in the plastic.

1 * 1 ethylene is polymerized by the Ziegler low-pressure process with the addition of 6 wt.% Hexantriol- (1.2.6). The polyethylene obtained is extruded into (I-shaped profiles, which are lined on the inside with rigid polyurethane foam.
Separation strength: separates in the foam

1.2 styrene is polymerized in aqueous emulsion free radical addition of 5 wt.% Pentaerythritol. The polystyrene obtained is converted into granulate form and processed by injection molding into containers which are lined with polyurethane elastomer.
The adhesion is excellent

1 * 3 maleic anhydride is condensed with a 20% excess of hexanediol (1.6). The polyester obtained is processed into plate-shaped elements by the hand lay-up process. These are on a continuously working double belt system; as described in DT-AS No. 1, 247.612, coated with rigid polyurethane foam

Separation strength: separates in the foam \ -

2 «Reactive agent incorporated into plastics processing.

2.1 A polyvinyl chloride paste in tricresyl phosphate is coated with 30% w / w triethanolamine, based on polyvinyl chloride, to form a film and gelled.

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Borrowed double belt system with rigid polyurethane foam coated.

Separation strength: separates in the foam.

2.2 A polyvinyl chloride granules in the mill with addition of 10 Gew.jS Ν, Ν, Ν, ¹ N '- (hydroxypropyl) - ethylenediamine rolled into a sheet. The strips cut from the fur are coated with flexible polyurethane foam Separation strength: separates in the foam

2 · 3 »Polypropylene granulate is processed into profiles in the extruder with the addition of 18 % glycerine. These are coated on one side with polyurethane elastomer.
Separation strength: excellent adhesion.

2 «4 · polyacetal polymer is mixed with 10% by weight of triethanolamine and extruded at 200 C. The molded body obtained is coated with flexible polyurethane foam. Separation strength: separates in the foam.

3 Surface impregnation in the course of molding production

3 · 1. An unvulcanized film made of ethylene propylene terpolymer

2
Rubber is coated with 10 g / m of tetraethylene pentamine

and then vulcanized The finished film is coated with rigid polyurethane foam
. Separation strength: separates in the foam

3.2. A terephthalic acid polyester fabric (Trevira, registered trademark of Hoechst AG) is impregnated with a polyvinyl chloride paste, the polyvinyl chloride layer is wiped off to the desired thickness _/ and then triethanolamine (8 g / m) is applied with a roller before gelling. The film obtained is called

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lower lamination material for the continuous production of rigid polyurethane foam elements on a double belt system, according to the DT-AS no. 1,247,612 used. Separation strength: separates in the foam.

3.3 Polyvinylidenchloridpolymerisat is extruded with 10 wt.% Dibenzyl as a plasticizer and 2-hydroxybenzophenone as Lichtschutznittel into a film, which is sprayed immediately after the exit from the extruder with a solution of diethylenetriamine in methylene chloride · The film is coated with polyurethane foam. > Separation strength: separates in the foam.

3 * 4 A polyvinyl chloride paste is spread on a textile fabric, pre-gelled at 80-100 ° C., then impregnated with pentaerythritol (20 g / ra) and fully gelled. The reinforced film obtained is coated with rigid polyurethane foam on a double belt system.
Separation strength: separates in the foam.

4. Surface impregnation of the finished molding.

4.1 A sintered polytetrafluoxethylene profile is heated and placed on it impregnated with diphenylmethane diisocyanate (15 g / m) Polyurethane elastomer adheres very well.

4.2 A glass fiber reinforced epoxy resin sheet is heated and after Impregnation with diethanolamine coated with flexible polyurethane foam: a well-adhering connection is obtained

4.3 A polyamide plate (polyamide-6,6 = polycondensate made from adipic acid and hexamethylenediamine) is heated, coated with glycerine (30 g / m) and then coated with rigid polyurethane foam: the adhesion of the polyurethane foam to the polyamide is excellent.

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In addition to the plastics listed in the examples, all other thermoplastics and thermosets can also be used for the purposes of the invention. This applies in particular to Acrylonitrile butadiene styrene polymers, acrylic rubbers, Acrylic ester-styrene-acrylonitrile copolymers, chloroprene rubber, Silicone rubber, fluororubber, polyacrylonitrile, polystyrene, polyvinyl acetate, polyvinyl fluoride, polyvinylidene fluoride, Polychlorotrifluoroethylene, ethyl cellulose, cellulose acetobutyrate, cellulose propionate, Cellulose acetate, polycarbonate, polyphenylene oxide, Poly phenyl sulfide, polysulfone, acrylic resins, alkylphenol resins, Allyl resins and aminoplasts.

The rigid polyurethane foams, flexible foams and elastomers detailed in the examples can be prepared in accordance with the current recipes, as described, for example, in the plastics manual volume 7 “Polyurethanes”, Karl Hanser Verlag, Munich 1966 _; be constructed·

You can choose between Polyurethanen.deren polyol component Polyester and between those whose polyol component a Polyether is different.

1 x polyester polyol

1.1 Soft foams: the polyesters used for this purpose are preferred wise linear or slightly branched adipic acid polyester ■ it has an average molecular weight of 1000 to 3000 and a hydroxyl number of 40 to 90. Let us take as an example here the Desmophen 2200 (registered trademark of Bayer AG), a polyester made from adipic acid and diethylene glycol

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and a little called trimethylopropane

1.2 Rigid foam: mainly highly branched polyester from Phthalic acid and adipic acid with a low average molecular weight (approx. 500) and an OH number between 150 and 400.

1.3 Elastomers: Linear, possibly slightly branched polyesters made from adipic acid and aliphatic diols. Average molecular weight around 2000 _y hydroxyl number 50-60.

2. Polyether polyols.

2.1 Soft foam: predominantly linear or triply branched Polyethers with an average molecular weight between about 1000 and 5000 and OH numbers between 32 and 60. Become a chain mainly ethylene oxide and / or propylene oxide used.

2.2 Rigid foam: mainly branched polyethers of lower Molecular weight with hydroxyl numbers between 300 and 1200.

2.3 Elastomers: mainly polytetrahydrofuran products are used, but also linear polypropylene glycols with an average molecular weight of 2000 and a hydroxyl number of about 60.

All commercially available diisocyanates can be used as the isocyanate component are used ^ for flexible foams in particular toluene diisocyanate, for rigid foams in particular diphenylmethane diisocyanate, for elastomers in particular ^ naphthylene-1,5-diisocyanate.

The production process for the polyurethane can be either a one-shot process or a prepolymer or Quasi-prepolymer processes can be used.

- patent claims -

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Claims (17)

- patent claims- 1.j Process for the production of a composite body from a V / molded body made of polyurethane and one from another Plastic, the reactant mixture forming the polyurethane molding is brought into contact with the plastic molded body prior to its complete reaction, characterized in that the plastic molded body, or the plastic that constitutes it, at least on the one to be connected to the polyurethane molded body Surface part with one opposite at least one component of the reactant mixture is impregnated or added to the reactive agent. 2. The method according to claim 1, characterized in that the reactive agent has functional groups which are Η-active, eg-oh, -sh,; nh, -nh ₂ , 5ch. 3. The method according to claim 1, characterized in that the reactive agent has functional groups which react with active H atoms, eg-NCO ^ NCS. 4. The method according to claim 1, 2 or 3, characterized in that that the reactive agent enters the plastic during its manufacture is added 5. The method according to claim 1, 2 or 3, characterized in that the reactive agent is added to the plastic during its further processing is added 6, The method of claim 4 or 5, characterized in that the plastic of about 3 to about 30 wt.% _T are preferably added to about 5 to about 15 wt.% Reactive agent. 7, method according to claim 1, 2 or 3, characterized in that
that the reactive agent is applied to the relevant surface part in the course of the production of the plastic molding 8 «The method according to claim 7, characterized in that on one possibly containing reinforcement inserts made of a woven, knitted fabric, fleece or the like made of textile, plastic or metal fibers, produced by painting or dipping from a polyvinyl chloride paste, ungelated polyvinyl chloride film by means of a roller or the like a uniformly thin film of the reactive agent applied, the polyvinyl chloride film gels and then, if necessary after cooling, with the polyurethane-forming reactant mixture, is preferably coated continuously, in particular according to the method according to DT-AS 1,247,612. 9. The method according to claim 1, 2 or 3, characterized in that
that the reactive agent acts on its surface part in question
of the finished plastic molding is applied. 10. The method according to claim 7, 8 or 9, characterized in that that on the surface of the plastic molded body about 5 to about 100 g / m, preferably
be applied. 2 2 100 g / m 2, preferably about 10 to about 30 g / m reactive agent 11. The method according to any one of the preceding claims, characterized characterized in that the reactive agent is multifunctional, preferably is at least trifunctional and has a molecular weight below about 500, preferably about 300. 609846/0884 12! · Method according to one of the preceding claims, characterized in that characterized in that the plastic molded body is made of a thermoplastic, e.g. polyvinyl chloride, polyethylene, polypropylene, polystyrene consists. 13. Composite body produced by one of the methods according to claim 1 to 9, characterized in that it is a sandwich element with a rigid polyurethane foam core and at least one outer skin made of plastic, e.g. polyvinyl chloride, polyethylene, polypropylene, polyester, ethylene-propylene rubber or the like is. 14. The composite body according to claim 10, characterized in that the plastic skin impregnated with the reactive agent has a water vapor pressure having. vapor permeability of at least 4 g / m according to DIN 53.122 15. The composite body according to claim 14, characterized in that the Plastic skin with a fabric, knitted fabric, fleece made of textile, plastic or metal thread is reinforced. 16. The composite body according to claim 10, characterized in that the The reactive agent used as an impregnating agent is also incorporated into the polyurethane as a crosslinking agent. 17. Composite body according to one of the preceding claims, characterized in that that the plastic skin partially protrudes beyond the edge of the rigid polyurethane foam core, so that an adjacent similar one Composite body is overlapped. 809 8 48/0884