DE2260199A1 - CONTINUOUS PROCESS FOR THE PRODUCTION OF POLYMER SHAPED BODIES - Google Patents

Description

JlEDTKE - BüHLING - KlNNE 2260199

TEL. (0811) 53 9θ53-5β TELEX: 524845 tipat CABLE ADDRESS: Germaniapatent Munich

8000 Munich 2

Bavariaring 4

P.O. Box 202403 December 0, 1972

Imperial Chemical Industries Linited London (Great Britain)

Continuous process for the production of polymer moldings "·

The invention relates to a continuous method of manufacture of polymer moldings that are themselves further deformable are.

In British Patent Nos. 1,272,984 and 1,279,673 are described, inter alia, Pol.ymerformkörper that continue are deformable or formable, and by partial implementation of a mixture of the precursors of a polyurethane and the prepro- ■ products of a cured polyester resin are produced. These molded bodies can be manufactured by conventional methods, e.g. by compression molding, draping over a i'oru or vacuum forming, further deform or form. Even after further deformation, the shaped bodies can be converted into hard or stiff shaped bodies be converted by reacting out the precursor mixture leaves.

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^C0PY BAD ORIGINAL

The subject of the invention is thus a method for the production of further-deformable molded bodies from ^ polymer material by partial conversion of a mixture of precursors or starting materials for the polymer material, based on the weight of the precursors,

a) 5 to 95 percent by weight of products of a polyurethane at least one polyfunctional compound with at least two groups capable of reaction kit isocyanate groups and at least one polyisocyanate

b) 95 to 5 percent by weight of precursors of a cured polyester resin of at least one ethylenically unsaturated polyester and at least one copolymerizable therewith, ethylenically unsaturated monomer,

which is characterized in that the flowable mixture of the preliminary products is applied to a moving carrier surface and in contact with this so extensively reacted or allowed to react that a manageable molded body is formed which can be further deformed.

The further deformable molded bodies can be shaped as desired be, however, are expediently planar shaped bodies with considerable strength, e.g. Plates, or thin, film-like structures or Foils. The invention is explained below with reference to the manufacture of panels.

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The polyurethane precursors contained in the precursor mixture are preferably essentially or completely free from ethylenically unsaturated bonds ^ and from the preliminary products of the cured polyester resin contain the ethylenically unsaturated polyester resin molecules preferably at least two groups that can react with isocyanate groups, so that J.er ethylenically unsaturated polyester with the polyisocyanate can react.

It is furthermore desirable that the mixture of precursors is homogeneous, that is to say that it is expedient to have none in the mixture Coarse phase separation visible to the naked eye can occur or should be present, although the possibility should not be excluded that a slight cloudiness in the mixture is available.

The polyisocyanate with isocyanate groups can be used in the intermediate product reactive groups containing polyfunctional Connection as well as with the ethylciiically unsaturated polyester, if this group is also reactive with isocyanate groups contains, respond. Furthermore, the ethylenically unsaturated monomer can with the ethylenically unsaturated groups of the polyester copolymerize.

The moving support surface can, for example, be a Gills or a band, e.g. an endless band ^ which is connected by a Variety of roles or rollers is carried. If a planar shaped body, e.g. a plate, is to be produced, then so

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_ Zj. _

It is recommended that the part of the tape that the mixture of Carries preliminary products, is itself supported in such a way that it forms a level, load-bearing pool. For example, this part of the Tape in turn be supported with a flat board so that the underside of the tape touches the board and from this will be carried.

The pre-product mixture, which can be applied intermittently or continuously to the carrier surface, must initially be sufficiently flowable or thin, i.e. have such a low viscosity that it dissolves quickly and distribute evenly on the support surface or quickly

distributed

and can be evenly on the support surface /. So it can be done before the preliminary product mixture is applied to the carrier surface the polyurethane precursors and the polyester resin precursors have already reacted to a certain extent which, however, must not have progressed so far that the viscosity of the preliminary product mixture has risen so much, that this can no longer be distributed quickly and evenly on the carrier surface. In view of this it should be expedient in particular, no too extensive reaction between the polyfunctional compound and the polyisocyanate have taken place before the precursor mixture hits the carrier surface is abandoned. It is about the fact that the conversion is too far-reaching and that the viscosity increases too much To prevent the latter two compounds are preferably only shortly before the precursor mixture on the support surface is applied and mixed together. If desired, the polyfunctional compound, dos Polyicocyanate, the ethylenically unsaturated polyester and dns

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Ethylenically unsaturated monomers just before application of the preproduct mixture on the carrier surface from separate Containers peeled off, combined and intimately mixed together, but it was found that it was right Satisfactory results are obtained if one considers the components of the Pre-product mixture is withdrawn from only two different containers, one of which is the polyisocyanate and among other things the other contains, among other things, the polyfunctional compound. The distribution of the product mixture on the carrier surface can be promoted by the fact that the mixture of precursors is brought into contact with one or more kneading rollers

or

brings and / from a transverse to the direction of movement of the carrier surface gives up on the support surface reciprocating nozzle.

The thickness of the intermediate product mixture layer on the carrier surface can, for example, by regulating the speed at which the preproduct mixture is fed in, by adjusting the width and the running speed of the support surface, by using a scraper or doctor blade or by squeezing of the pre-product mixture can be set on the carrier surface. Expediently, the thickness produced according to the invention is ter panels up to 12.7 mm or more. The thickness of the panels is preferably in the range of "1.59 to 6.35 mm.

If the preproduct mixture on the carrier surface is so thin is that it tends to call down from this one, the support surface can be provided with devices that

3 0 9 0 2 6/1 0 4 β

-e- 2280199

hold back the precursor mixture and prevent it from the carrier surface flows off. For example, if a tape is used as the carrier surface, it can also expediently be used be equipped on his or in the vicinity of his side edges arranged walls or sealing collars. The walls can at the same time serve to regulate the width of the panels to be produced.

After the pre-product mixture has been applied to the carrier surface, the pre-products should react with one another to the extent that in order to obtain a rapidly deformable plate.

It is desirable, but not necessary, for the precursors to react with one another to such an extent that a non-sticky plate arises. The implementation should proceed at least so far that the panels produced are manageable, i.e. self-supporting or self-supporting and are no longer so fluid that they flow substantially under their own weight; On the other hand, the unsettling should has not yet progressed so far that the plate can no longer be deformed further. It is desirable that the The panels obtained are so flexible that they can be deformed by hand, e.g. draped by liand over an i'orm or a model can.

A suitable degree of reaction can be determined on the basis of a simple experiment be selected, however, it was found to be is useful to obtain a further deformable plate when the stakt; finding implementations go so far, that the polyfunctional compound and the ethyleneically unsaturated one Polyester, if this is functional with isocyanate groups

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contains capable groups, essentially completely with the Polyisocyanate reacted while between the ethylenically unsaturated monomer and the ethylenically unsaturated polyester essentially no interpolymerization should have taken place ..

The reaction of the mixture of precursors on the surface of the carrier can be regulated by regulating the temperature and through the use of catalysts and inhibitors. For example the reaction of the polyisocyanate with .the polyfunctional compound as well as with the ethylenically unsaturated polyester, if this contains groups that are reactive with isocyanate groups, urethane catalysts known to the person skilled in the art, such as tertiary amines and metal salts, e.g. tin (II) octoate and dibutyltin dilaurate, and the copolymerization of the ethylenically unsaturated monomer with the ethylenically unsaturated polyester

free

by suitable / radical-generating substances, e.g. peroxides and Azo compounds, are catalyzed. If desired, the Copolymerization by using suitable inhibitors for I can inhibit radical reactions, e.g. quinones. However, since the above-mentioned reaction is generally at relatively lower temperatures, but the above-mentioned copolymerization usually at a relatively high temperature, in the process of the invention it is by far preferable to keep the temperature during the time in which the pre-product mixture is in contact with the carrier surface, so that the polyurethane pre-products are in contact with one another as well as with the ethylenically unsaturated polyester, if this

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contains isocyanate-reactive groups, at least to the extent that a manageable plate is obtained, and preferably react essentially completely, while essentially no interpolymerization between the ethylenic unsaturated polyester and the ethylenically unsaturated monomer takes place.

If catalysts, e.g. urethane catalysts and free radicals Generating substances and inhibitors are to be used, so you can incorporate them into the precursor mixture before it is on the carrier surface is abandoned.

Even if the reaction of the polyurethane precursors is involved and optionally with the ethylenically unsaturated polyester at relatively low temperatures, e.g. at Room temperature or close to the ambient temperature.

but

low temperature, it is advisable to heat the precursor mixture on the support surface to such an extent, for example to at least 50 ° C., that this reaction proceeds as quickly as possible without causing a significant degree of copolymerization at the same time, whereby , preferably the temperature is chosen so that the ethylenically unsaturated monomer copolymerizes only to a small extent, if at all, with the ethylenically unsaturated polyester. Suitably, the temperature of the Vorproduktgemisches is held on the carrier top spells at 8O ⁰ C.

If a copolymerization takes place at all, this should in any case not lead to the fact that a plate is obtained which

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1 BATH

can no longer be deformed further.

The reaction on the carrier surface can be initiated by heating regulate the existing preliminary products particularly well. Therefore, the precursor mixture is preferably at a temperature abandoned on the moving support surface, which is below the one in which there is a substantial conversion between the polyfunctional compound and the polyisocyanate, as well as, if the polyester contains groups that are reactive with isocyanate groups, the ethylenically unsaturated polyester takes place, and the reaction is initiated by regulating the heating of the mixture of precursors moving with the support surface and regulated. Suitable heating devices are hot plates and radiant heaters.

In order to be able to easily remove the plate from the support surface, it is desirable that 'the material from which the support surface consists, not of the mixture of preproducts given on it generated Plabtc adheres. It was found that. as a material for an εIs carrier surface to be used tape including silicone rubber and polyalkylene terephthalate, in particular polyethylene terephthalate in the form of a "Helinex film" (Melinox is a registered trademark of InvDerial Chemical Industrios Ltd.). A rubber band is expediently used as the band for the purposes of the invention, dns with is coated with a polyethyleneterephthalate film.

In accordance with the invention, handleable products produced on a support surface

BAD ORiGlNAU

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Plates can be removed from the support surface. For example, the panels can be cut into sections suitable for storage or rolled up for storage. Optionally, you can leave the handleable plate on the support surface and store it together with the support surface, for example in the form of a hulk. In this case, the plate, if it is used for the production of moldings ¹ , can be removed from the carrier surface. This mode of operation is particularly useful when a film-like material, for example made of polyethylene or polyethylene te: ephthalate, is used as the carrier surface, since the layer of film-like material prevents the individual layers of the Stick the plates together in the roll.

When a film-like material is used as the carrier surface is in turn supported by a carrier, e.g. a belt or belt and in particular an endless belt or be worn.

In order to reduce the formation of air bubbles in the pre-product mixture applied to the carrier surface, it is advisable to to degas the precursor mixture before it is applied to the carrier surface. It is also recommended to apply the pre-product mixture to a surface inclined downwards in the direction of movement of the carrier surface and to transfer it over to allow this inclined surface to flow down onto the moving support surface. Preferably the bottom edge of the grinds inclined plane on the moving support surface. Purpose-

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moderately, as the inclined surface, one supported with a beam becomes film-like material, e.g. a polyethylene terephthalate film, used.

The formation of bubbles in the plate can be reduced even further by placing them together with or on the carrier surface moving plate squeezes. If, for example, the support surface is a belt or belt, or one carried by a belt film-like material is used, the plate can be sandwiched between two belts, e.g., an upper and a lower Band, the distance of which sj-cii gradually decreases, are squeezed.

When used, the plate can be made of polymer material be deformed by methods known per se. For example, the plates can be compression molded using a mold or model draped or formed by yakuum deformation. The l'Ormgebung can be supported by using V / ärme. After the further 'shaping of the plate, the implementation of the preliminary product mixture substantially completed, e.g. d. by copolymerizing the ethylenically unsaturated monomer with the Ethylenically unsaturated polyester. The copolymerization can be carried out by heating the further deformed IB molded body, preferably in the presence of a catalyst, e.g. a substance which generates free radicals, \ tfie a peroxide, or by irradiation in In the presence of a suitable photosensitive catalyst. The catalysts used in the Carrier surface applied preproduct mixture be present

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are useful in amounts of 0.01 to 5 percent by weight, based on the total weight of the preliminary product mixture.

Kit isocyanate reactive groups in the polyfunctional Compounds can be, for example, amino, hydroxyl and carboxyl groups. Ethylenically unsaturated polyester can contain, for example, hydroxyl and carboxyl groups as groups which are reactive with isocyanate groups.

The polyfunctional compound and the polyisocyanate can both be difunctional compounds. In these) I ¹ 'a 1.1, the polyurethane precursors can form a linear polyurethane. On the other hand, the polyfunctional compound and / or the polyisocyanate can contain more than two functional groups, in which case the polyurethane precursors can then form a crosslinked polyurethane.

In view of the fact that the molded body produced from the board by complete conversion of the precursor mixture has desirable properties, polyurethane precursors are preferably used which, if they are reacted with one another in the absence of the polyester resin precursors used in combination to produce the board, form a polyurethane with a glass rubber transition temperature of at least 25 and preferably at least 35 ⁰ C can form.

Polyfunctional ones useful in the process of the invention Compounds, polyisocyanates, ethylenically unsaturated poly-

309826/1046 bad original

Ester and ethylenically unsaturated monomers are in the British Patents 1,272,984 and 1,279,673 described, to which reference is hereby made. ± '' for the purposes of the invention can be any combination of the cited patents pre-products described are used.

Suitable polyfunctional compounds are, for example, polyols, such as polyether polyols, and polyesters, especially polyester, which essentially exclusively contain hydroxyl groups as closing groups.

Examples of suitable polyols are glycols of the formula HO-R-OiI I ₁ -

in which R is, for example, an alkylene radical, such as ethylene glycol, Propylene glycol, butane-1,4-diol, pentane-1, ^ - diol, Mexan-1,6-diol, diethylene glycol and dipropylene glycol. Other suitable polyols include polymers derived from glycols, preferably of low molecular weight, e.g. Polyethylene glycol, Polypropylene glycol and polybutylene glycol. Suitable polyols with three or more functional groups are for example glycerine, pentaerythritol, keopentyl glycol, trialkylolalkanes, such as trimethylol, triethylol and ÜJributylolpropane, as / he alkoxylated derivatives, especially those of low molecular weight, of trialkylolalkanes, e.g. ethoxylated or propoxylated to trimethylolpropane. I'for the purposes Glyceral alkoxylation products, for example propoxylated glycerol derivatives, especially those with, are also suitable for the invention

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low molecular weight.

For the purposes of the invention, diols with aromatic groups, e.g., diols of the formula

HO - <^ X) -X- ^ ^ - OH II,

in which X is a direct bond or a divalent radical, for example a jiest of the formula -SOp- or -0- or an optionally hydrocarbon-substituted, alkylene radical of the formula - (CH ₂ ) _n -, in which η is an integer, preferably in a range of 1 to 4 can be used.

A preferred diol is 2,2'-bis (p-hydroxyphenyl) propane formula

CH ₅

HO - <( \> - C - </ ^ - OH III

CH-,

or an alkoxylated, e.g., ethoxylated or propoxylated Derivative of this compound.

Examples of suitable polyesters include condensates of at least one diol of the I / orrnel I and at least one Dicarboxylic acid of the formula

HOOC - H - COOH IV,

in which R denotes, for example, an alkylene chain which can be the same or different in the diol and in the oleic acid. Examples suitable

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Neter polyesters are folyethylene adipate, polyethylene sebacate, Polyethylene annealing agent, polyethylene pimelate, polypropylene adipate, Polypropylene sebacate, polypropylene glutarate and polypropylene pimelate. Worth mentioning polyester with more than two functionalities Groups include condensation products of adipic acid with glycerol and either ethylene glycol or propylene glycol, as well as condensation products of adipic acid with trimethylolpropane and either diethylene glycol or propylene glycol.

As the diisocyanate component Polyurethonvorprodukte example, aliphatic, aromatic or cycloaliphatic diisocyanates or diisocyanates ^T ~ can erwendct iverdon that an aromatic and an aliphatic isocyanate, an aromatic and cycloaliphatic group or an aliphatic. · Or contain 'a cycloaliphatic group.

As examples of the diisocyanate components of the polyurethane precursors suitable diisocyanates are 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,4-toluene diisor cyanate, 2,6-toluene diisocyanate and mixtures of the toluene diisocyanates mentioned to call.

When the manufactured by completing the implementation of the preliminary products Moldings which should have high impact strength and good bending properties are preferred as diisocyanates those of the formula

HCO · RCO

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where X is a two-valued best. For example, X can be a group of the formula

VI

be, in which η is an integer, and preferably an integer from 1 to 3, and R ^, and Hp are identical or different and each represent a hydrogen atom or a hydrocarbon radical, for example an alkyl radical such as the methyl radical. A preferred diisocyanate is H , 4'-diphenylmethane diisocyanate.

The ethylenically unsaturated polyester can, for example, by Esterification of an unsaturated dicorbonic acid or a mixture of such acids with a saturated glycol or a mixture such glycols or by esterifying a saturated dicarboxylic acid or a mixture of such acids with an unsaturated one Glycol or a mixture of such glycols. If desired, one or more unsaturated ones can be used Acid (s) in combination with or instead of one or more saturated acid (s) and one or more unsaturated (s) Use glycol (s) in combination with or instead of one or more saturated glycol (s). Instead of The corresponding dicarboxylic acid can also be used as the anhydride v / earth. .Examples of unsaturated polyesters are, among others those by esterifying maleic, fumaric or itacpnic acid, mixtures of the acids mentioned with one another and / or with saturated dicarboxylic acids with glycols, e.g. ethylene, propylene or

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Butylene glycol, mixtures of the glycols mentioned with one another and / or products made with other dihydric alcohols. Particularly noteworthy are unsaturated polyesters Condensates of isophthalic acid and fumaric acid with propylene glycol, Condensates of maleic anhydride and phthalic anhydride with propylene glycol and optionally either diethylene glycol or adipic acid, and condensates of propylene glycol with fumaric acid or maleic acid, and optionally also with Phthalic anhydride.

Examples of suitable ones with the ethylenically unsaturated groups the polyester copolymerizable monomers are among others Vinyl monomers such as vinyl esters, aromatic vinyl compounds and vinylniti * ile. Suitable vinyl esters include, for example Vinyl acetate and acrylic acid esters of the formula

CH ₂ = CH - COOR ₂ ·. VIl,

in the r _? is an alkyl, aryl, alkaryl, aralkyl or cycloalkyl radical. Rp can be, for example, an alkyl radical with 1 to 20 and preferably 1 to "10 carbon atoms. Specific vinyl esters r.ind inter alia, for example, kethyl acrylate, <.. thylacrylate, n- and iso-propyl acrylate, as well as n-, iso- and Mentioning tert-butyl acrylate.

Other suitable vinyl esters include, for example, "esters of the B 'formula

Ch ₂ = C (U ₃ ) COOR ₂ VIII,

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in which R 1 can be an alkyl, aryl, alkaryl, arolkyl or cycloalkyl radical. In the case of the esters of the formula VIII, Rp and R ₇ can be identical or different. Examples of special vinyl esters that may be mentioned include methyl methacrylate, ethyl methacrylate, n- and iso-propyl methacrylate and n-, iso- and tert-butyl methacrylate.

Aromatic vinyl compounds include e.g. styrene and styrene derivatives such as Λ-methylstyrene and vinyl toluene, to mention.

Suitable vinyl nitriles include, for example, acrylonitrile and its derivatives such as methacrylonitrile.

Polyfunctional vinyl monomers, i.e. monomers that have two or more containing more vinyl groups are also suitable.

Suitable monomers include, for example, glycol dimethacrylate, Divinyl benzene and diallyl phthalate.

The proportion of monomer copolymerizable with ethylene unsaturated polyester to ethylene unsaturated polyester in the precursors for the cured polyester resin can be, for example, in a range from 30 to 90 percent by weight of at least one ethylenically unsaturated polyester to 70 to 10 percent by weight of at least one monomer copolymerizable therewith. Said preliminary products preferably contain 50 to 70 percent by weight of at least one aesthetically unsaturated polyester and 50 percent by weight.

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cent of at least one monomer copolymerizable therewith.

The properties of the complete reaction of the po-

polyurethane precursors and the precursors for the cured molded body obtained

Polyester resin / depend on the proportions in which the individual pre-products are contained in the pre-product mixture used to manufacture the panel. For a good combination of properties, e.g. flexural properties and impact strength, the pre-product mixture should preferably contain polyurethane pre-products and pre-products for cured polyester resin in a ratio that is in a range from 20:80 to 80:20 percent by weight and preferably in a range from 30 to 70 to 70 ^: 30 percent by weight, and in particular in a range from 40: 60 to 60: 4-0 percent by weight.

The molar ratio of isocyanate groups to reactive groups Groups in the pre-product mixture can expediently be in a range from 0.8: 1 to 1.2: 1, but can of course also be Outside the specified range and in particular molar ratios of isocyanate groups to reactive groups Groups are applied that are considerably smaller than 0.8: 1 are.

Panels made by the method of the invention may contain particulate filler material. Such filler materials, which result in a reinforcement of the moldings produced by reacting the precursors, are, inter alia, for. B. talc, sand, titanium dioxide, clays and calcium carbonate. For the purposes of the invention, those skilled in the art can use as fillers for

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Polyester resins known particulate fillers are used will.

Expediently, the particulate filler material can be used or more of the precursors contained in the preproduct mixture or add the preproduct mixture before this on the moving 'carrier surface · is abandoned. Usually be at least 5 and up to 70 percent by weight, based on the Total weight of particulate filler material and Pre-product mixture, particulate filler material used.

The panels can also be stripped of fibrous material in order to go through complete. Implementation of the pre-product mixture produced therefrom Reinforce molded body. In the bars have such 'shaped bodies compared to standard bodies that do not contain any fiber material, better impact strength and better flexural strength on. Suitable fiber materials include glass, e.g. in the form of mats, fabrics, staple fiber or continuous filament, asbestos, Carbon and fibers made from an organic polymer material such as nylon or polyethylene terephthalate. Usually amounts to the amount of fiber material used at least 5 and up to 70 percent by weight, based on the total weight of! '' ascrmaterial and preproduct mix.

In the Hegel the fiber material is added to the primary product, after this has been posted on the carrier surface is. About the distribution of the fiber material in the preliminary product to promote, the fiber material and the pre-product mixture

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be kneaded on the [Dräger surface, e.g. with kneading rollers. The fiber material should be added to the pre-product mixture, before the preliminary products have reacted with one another to such an extent that the fiber material can no longer penetrate the mixture. A preferred method for incorporating fiber material into panels produced according to the invention is that one applies a mixture of precursors as described above to two moving support surfaces, the fiber material with at least one of the two located on the 'carrier surfaces Brings preproduct mixtures into contact and which the 'Vorprodukbgemischen supporting carrier surfaces so that between the carrier surfaces a sandwich structure of Vor-'oroduktgoiriisch and fiber material is created »This Arbeilswcinc is particularly useful when the support surfaces consist of two / one tapes or film-like materials that of two Belts or straps worn v / ground. In this case it is special zv / angular to process the belts with kneading clay to support the distribution of the fiber material. Farther the above-mentioned method is particularly useful when the plate is both divided material and fiber material should contain, since it can be difficult for the fiber material to penetrate into a Vorproduktgomisch that also divided Contains material because such a mixture can be highly viscous. In this case, the use of kneading rollers is very special to recommend.

If the plate is both fibrous material and divided or granulated Should contain material, depends on the amount of fiber material,

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which can be used appropriately if, for example, good wetting of the fiber material is to be achieved by the preliminary product mixture, among other things on the amount of granular material used in each case. So it will be with a given man. gen amount of fiber material more and more difficult to wet this satisfactorily, the more granular material is used. Accordingly, it is becoming increasingly difficult with the use of a given quantity of granular material, to wet the fiber material satisfactory, _t ie greater the amount of fiber material is used.

If the plates are to contain both divided or granular material and fiber crumbs, they are preferably used Up to 60 and in particular 10 to 60 percent by weight of granular material, based on the total weight of the granulated Material and the precursor mixture, and up to 50, preferably 10 to 50 and in particular 10 to 30 percent by weight of fiber material, based on the total weight of fiber material and pre-product mixture.

In the production of panels containing fiber material and in particular panels that contain both fiber material and contain divided material, the precursor mixture is preferably heated on the carrier surface to partially

l,

Implementation of the preliminary products to the desired extent. It was found that. by heating the pre-products the extent, to which the fiber material in the plate of the pre-products is wetted, compared to a plate that after a

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Method in which no heating is applied is established is improved. Accordingly, the properties of a standard body produced from a plate produced in this way by the reaction of the preliminary products contained therein are usually improved. Eg is advantageous to heat the precursors at least 4-0 and preferably at least 50 ⁰ C, but it should-eighth, is ensured da3 "that the reaction caused thereby does not go as far as the precursors to obtain a plate In particular, when the polyfunctional compound is reacted with the polyisocyanate and, if the polyester contains isocyanate-reactive groups, the ethylenically unsaturated polyester for the production of the panels, care must be taken to ensure that as a result of the No or only slight copolymerization of the ethylenically unsaturated monomer with the ethylenically unsaturated polyester takes place on heating.

The plates can contain other additives, e.g. antioxidants, Ozone protection agents} contain UV stabilizers and color pigments, the mixture prior to application to the carrier surface can be added. According to a particularly preferred embodiment, the plates are given a release agent, e.g. zinc clay incorporated, so that the removal of the standard bodies produced from the plates from the mold is facilitated.

After the! Processes of the invention can also be laminates as panels with a layer of another moldable polymer core

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rial or laminates are produced in which the invention manufacturable plates are laminated on both sides with a layer of a different polymer material, wherein the two cover layers can be the same or different. The polymer material layers can be made from a thermoplastic Polymer consist that can be deformed by, for example, the layer (s) of thermoplastic polymer by heating softens.

The laminate can be made hot by, for example a pre-product mixture as described above on a layer of moldable polymer material forming the carrier surface brings up. The layer of moldable polymer material can itself be supported by a carrier, for example a tape, such as a endless belt as described above can be supported. The plate in the manufactured by the method of the invention As described above, laminate can be particulate Contain material and / or fiber materials.

Suitable thermoplastic polymers include polyolefins, e.g. polyethylene and polypropylene, polyvinyl halides, e.g. polyvinyl chloride, acrylonitrile-butadiene-styrene copolymers and acrylic polymers such as polyacrylonitrile and polymethyl methacrylate.

The invention is illustrated below with the aid of examples.

In Examples 1 to 5, the in Figures 1 and 2 of

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The device shown in the accompanying drawing is used. Figure 1 shows a schematic representation of this device and Pigur 2 shows a partial perspective view of the FIGS gur 1 shown device.

The device has a double-walled container Λ made of mild steel, which has a capacity of 90.92 liters. A heating fluid can be circulated between the walls of the container. The container 1 is equipped with a stirrer, an electrical heating device, a thermocouple for measuring the temperature, an outlet through which it can be evacuated, a nanometer for measuring the prevailing negative pressure, an inlet opening through which it is charged with reactants and through which an inert gas can be fed and an outlet through which the reactants can be withdrawn. A second, single-walled mild steel container 2 with a capacity of 22.76 liters is also provided, which is the same as container 1, but is also equipped with a thermostat.

A nylon tube 3 leads from the outlet opening of the container 1 an outer diameter of 12.7 mm and an inner diameter of 9.53 mm to a Savery Pump 5 (Viking Engineering Co. Ltd.), those with a device for adjusting the flow rate equipped. is. A nylon tube 4 also leads from the outlet opening of the container 2 to a second Savery pump 6. The nylon tubes 3 and 4 are covered with flexible polyurethane foam.

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A sheathed nylon tube 7 leads to a three-way valve 8, from which leads a sheathed nylon return pipe 9 to the container 1 and a sheathed nylon pipe 10 to a mixing head 15. On analog Way leads from the Savery pump 6, a sheathed nylon tube 11 to a further three-way valve 12, one of which is sheathed Nylon return pipe 13 to container 2 and a sheathed Nylon tube 14 leads to the mixing head 15.

From the mixing head 15 (Viking Type B, Viking Engineering Co. Ltd.) » which is equipped with a heating jacket, leads a covered one Nylon tube 16 to a nozzle 17 made from a copper tube with an inner diameter of 12.7 mm. This nozzle 17 is in a block 18 made of aluminum, supported by the .sie extends. The block 18 has two bores and is; on two otahlstäben 19, 20 movably mounted. The block 18 isb on an air cylinder (Martonair Go. Ltd.) (not shown) attached, with which it can be guided back and forth on the steel rods 19 and 20. The stroke of the block 18 on the Ütahlstäben 19 and 20 is controlled by two stop microswitches (not shown).

The nozzle 17 is arranged above a plate 21 made of aluminum, which is inclined at an angle of 4-5 to the horizontal. The plate 21 has a horizontal width of 91.44 cm and in Slope of 45 ° a length of 20.32 cn. The plate 21 is with a polyethylene terephthalate film 22 (ftelinex, Imperial Chemical Industries Limited). The Melinex foil 22 touches another Melinex film 23, which is drawn from a roll 24-

309826/1046

and is arranged on an endless conveyor belt 25. The film 23 runs to a roll 26. The conveyor belt 25 is 0.79 mm thick and 91.44 cm wide, consists of glass fiber reinforced silicone rubber and rests on a 121.9 cm wide, flat support plate 27. The conveyor belt has 9.53 mm high sealing collars on its edges and runs around corrugated rollers 30, 31 with a diameter of 30.4-8 cm which are arranged at a distance of 914.4 cm. Below the Stutsplatte 27, the conveyor belt 25 is supported by tension rollers 32, 33 ₅ 34- with a diameter of 10.16 cm and runs through a conveyor belt guide device, * which consists of a pair of rollers 35 »36 with a diameter of 10.16 cm each and a feeler (not shown) (available from Mount Hope Machinery Ltd.) adapted to guide conveyor belt 25 on rollers 30 and 31. The target 30 is driven by a motor 37 and a gear unit, which has a continuously variable speed control; permitted (available from Allspeeds Ltd.) powered. To receive the plate produced by the method of the invention from the conveyor belt 25, a spindle driven by the motor 37 and the gear unit via a slip clutch is provided with a diameter of 15.24 cm.

To carry out the method of the invention, the container 1 with polyisocyanate, ethylenically unsaturated polyester and Ethylenically unsaturated monomer charged. The container content is stirred and the container 1 is charged with polymerization catalyst and evacuated to a pressure of 254 Torr and 1 f> Held under this pressure for minutes. Then the vacuum is filled.

309826/1046 * ■

Container 1, wherein nitrogen is allowed to flow into the container and the contents of the container are kept at a temperature of 25 ° C.

The container 2 is charged with a polyfunctional compound and urethane catalyst, whereupon its contents are heated to 100.degree. C. and the container 2 is evacuated to a pressure of 762 Torr, which is kept constant at this value for two hours.

Then allowed to nitrogen in the holding] - 2 flow and decreases the temperature to 6 ° ^r i G. So that yourself; heat the tubes 4 and 11, the pump 6 and the valve 12 to the temperature of the contents of the container 2, the pump 6 is started and for 10 minutes the contents of the container 2 are drawn off through the tube 4- and via the 1; ohrc 11 and 15 and the three-way valve 12 in the circuit / to container 2 returned.

The contents of the container 1 and 2 are then pumped in each case at the desired speed to the mixing head 15, which is heated ^{to c) 0 C.}

From the mixing head 1 ', the streams, which have now been mixed with one another, are conveyed from the iiohältern 1 and 2 to ¹ nozzle 17 and emptied from this onto the layer of Hciincx film 22 arranged on the dor poneipten plate 21. The nozzle 17 holds

y "

Block 18 is placed on the steel rods 19 and 20 with the desired

Frequency passed back and forth. -., ■ -, -

The mixed streams (Vovproduktpomisch) flow over the

309826/1046

»29 -"

2260139

Melinex film 22 down onto the one on the conveyor belt 25 Melinex ^ slide 23, the conveyor belt 25 and the Melinex slide are moved at the desired speed in the direction in which the end of the Melinex film, 22 lies on the P1elinex FQ 23 tows.

The Varproduktgemiseh is distributed on the conveyor belt 25 arranged Helinex film 23, and when walking through the conveyor belts react the polyigoeyanate, the OoIy * - functional connection and the ethylenically unsaturated polyester to a non-sticky, flexible and pliable Plate that is at the end of the conveyor line of the conveyor belt 25 of the Melinex film 23 is removed and wound onto the spindle 38 "

example 1

tJach the method described above using 13.28 kg vjurde ^ - ^ '- Diphenylmethandiisocyanet as polyiso · "cyanate, the -5 ° G was preheated to 40 to ^Z, 9.9 kg of an ethylenically unsaturated polyester having a Hydroxylwcrt! of 40.3 mg KOH / g and an acid value of 4.5 mg KOH / g, which had been prepared by condensing propylene glycol with fumaric acid and isophthalic acid (fumaric acid / isophthalic acid molar ratio = 3: 1), 6 , 2 kg of styrene as ethylenically unsaturated

I.
tes monomer, 200 g tert-butyl peroxide as Polyinerisn-uj.onskoto-

'} ■
lysotor, .200 g dibut ^ yl ^ inndilaurat as urethane catalyst and a mixture of 1.6 kg propoxylated B: ispher> ol-A with a hydroxyl value of 333 mp; KOH / g and 9.12 kg of a l'oüyesterpplyols with a Stiureweri. of 1 mg KOH / g and a hydroxy L value

3Q982-.6 / 1046

of 545 mg KOH / g, obtained by condensing adipic acid with Glycerin and diethylene glycol in a molar ratio of 3: 1 | 23: 6.7 had been produced, a flexible, dige plate made of 60 percent by weight of polyurethane precursors and 40 percent by weight of precursors for the cured polyester resin made φ

The contents of the container 1 at a rate of 2.28 kg / minute and that of the container 2 at a speed ' speed of 0.83 kg / minute is pumped via the mixing head 15 to the nozzle 17. The block 18 was made with a frequency of 15 cycles, i.e. 30 crossings per minute back and forth, the conveyor belt 25 ran at a speed of 121.9 cra / kinute,,

The resulting 4.76 mm thick and 91.44 cm wide plate was flexible and pliable and could be deformed by hand draping over a shape or model.

In order to fully cure the flexible plate, it was made from it square specimens with an edge length of 30.48 cm pressed in a 4.76 mm deep mold and in a hydraulic press Heated to 130 G for 2 1/2 hours. Then the was obtained thereby Remove the stiff and half-shaped plate from the mold. The rigid plate thus obtained had the following property ^ on:

309Θ26 / Ί046

Hot deformation temperature 104 C, flexural strength 1285 kp / cm ²

Flexural modulus 30.970 kg / cm ²

Gharpy impact strength notched 6.6 kgf cm / cm

unnotched 24.6 kgf cm / cm

The V / arm deformation temperature was according to ASTM D 648/56

kp / cm).

Flexural modulus and strength were measured with; a formation speed of 1 ^ / minute using test objects with the dimensions 76.2 χ 12.7 x 4.76 mm and with a clamping width of 50.8 mm measured on a "Hounsfield Tensometer".

The impact values were measured on a Kounsfield impact tester on "non-notched specimens with dimensions 50.8 χ 6.35 x 4.76 mm.

The notched impact strength values were the same on irons Dimensions determined that in their side with the dimensions 50.8 χ 6.35 mn a 3.18 mm deep notch cut with a notch radius of 0.254 min.

Example 2

Analogously to Example 1, a flexible, pliable sheet was made from 40 percent by weight of polyurethane precursors and 60 percent by weight of precursors prepared for the cured polyester resin, with the deviation from Example 1, the container 1 with the ethylenic unsaturated polyester, styrene, propoxylated

_: § j; - 3 0 9 -2 & A \ Q * k. BATH ORIGINAL

Bisphenol-A and the urethane catalyst and the container 2 with the polyisocyanate and the polymerization catalyst, omitted the polyester polyol, tin-II octoate as the urethane catalyst, tert-butyl perbenzoate as the polymerization catalyst and a 4,4'-diphenylinethane diisocyanate containing polyisocyanate with a Isocyanate functionality of 2.7 to 2.8 (Suprasec DN ₁ Imperial Chemical Industries Limited) was used.

The precursor mixture components were in the following amounts used:

Ethylenically unsaturated polyester 7.4-4 kg;

, Styrene 4.56 kg;

Polyisocyanate 3.04 kg;

propoxylated bisphenol-A 4.96 kg:

Tin (II) octoate 100 g;

tert-butyl perbenzoate 100 g

The pumping speeds from containers 1 and 2 were respectively 1.145 or 0.21 kg / day. The running speed of the conveyor belt 25 was 60.96 cm / minute.

The 'and η ° / 1' thus obtained 3.18 mm st ^ τ · ^1! '4 cn wide flexible, supple plate was prepared by compression molding at 125 ° C during 15 minutes a j.rog with base dimensions of 30 , 48 χ 30.48 cm and 2 ", 54 cm high walls molded«

309826/1046

- 33 -

Example 3

Example 2 was repeated to prepare a flexible, .geschmeidigen plate / having a thickness of 3,13am and a width of 45 _r 72 cm, said deviating thereof ', the container or 2 as follows were charged:

Container 1:

Ethylenically unsaturated polyester 1.30 kg; Styrene .0.8 kg ;.

Tin (II) octoate 20 g;

Polyester polyol as in Example 1

(instead of the propoxylated bisphenol-A) -Q, 875 "kg.

Bell senior 2:

Polyisocyanate (as in Example 2), 0.525 kg;

tert-T-butyl peroxide (instead of the tert ^ butyl perbenzoate) 20 g «

The pumping speeds from the containers 1 and * 2 were 0.82 and 0.15 kg / minute, respectively. The distance between the sealing collars or lips 28 and 29 was 4-5.72 cm, their height 3.18 mm and the running speed of the conveyor belt 25 was 60.96 cm / minute.

A sample of the plate thus obtained was molded by compression molding under the same conditions as in example 2 to a dimensionally stable, dome-shaped molded body with a diameter of 15.2 ^ cm at the base of the dome and a height from the base processed to the apex of the dome of also 15 »24 cm.

Example 4-

Analogously to Example 1, a 3.18 mm thick and 45.72 cm wide was made

309826/1046

flexible, pliable sheet made of 50 percent by weight polyurethane precursors and 50 percent by weight of precursors for hardened products Polyester resin using the following starting materials and produced using the following pumping speeds:

Ethylenically unsaturated polyester 1.3 kg;

Styrene 0.8 kg;

4,4'-diphenylmethane diisocyanate 1.18 kg;

Polyester polyol 0.78 kg;

propoxylated bisphenol-A "0.138 kg;

tert-butyl peroxide 20 g;

Dibutylζinndilaurat 20 g;

Pumping speed container 1 0.80 kg / minute; ¹¹ container 2 0.227 kg / minute.

The running speed of the conveyor belt 25 and the distance and the height of the sealing collars 28 and 29 corresponded to Example 3

The plate removed from the conveyor belt was flexible and pliable and could be easily stretched and molded into various shaped articles.

As in Example 2, a sample of the plate was shaped into a trough or tub and cured.

example 'p

Example 4 was used to make a flexible, pliable

309826/1046

Plate made from 4-0 weight percent polyurethane 'primary products and 60 percent by weight of precursors for the cured polyester resin using the following starting materials and application the following pumping speeds repeated:

Ethylenically unsaturated polyester 2.6 kg;

Styrene x -1.6 kg;

^ -, V-piphenylmethane diisocyanate 1.61 kg;

Polyester polyol 1.06 kg; propoxylated bisphenol-A _t 0.176 kg;

tert-butyl peroxide 30 g;

Dibutyl tin dilaurate 60 g;

Pumping speed container 1 0.90 kg / minute; "Container 2 0.198 kg / minute.

The plate removed from the conveyor belt was flexible and pliable and could be easily stretched and molded into various shaped articles.

A sample of the plaite was analogous to Example 2 to a trough or molded and hardened in a tub.

To carry out the following Examples 6 to 9, the

the
used in / 3 and ¹ V wiodcrgefrcbene device. Figure 3

Koigt a schematic view of the device and Figure A- a perspective .Ansicht of the device shown in Figure 3.
The ^{device shown in FIGS. 3 and} 5 closes the containers shown in FIG. 1 as parts 1 to 16

2 ^ / 1.0 46 BAD ORJ _GiNAt

Pump systems, however, these device parts are in the figures 3 and 4 not shown. In the device shown in Figures 3 and 4, instead of the mixing head 15, the The device shown in FIG. 1 is a Kenics static mixer and are instead of the nozzle 1? two nozzles 39 and 40 are provided, which from Mixer 15 via the uiran-coated nylon tube 16 can. The device according to FIGS. 3 and 4 has two rollers 24, 42, each carrying an Im wide polyethylene film, the nozzles 39.40 arranged over the foils 23 and 43, respectively; are. Another nozzle 41, through which chopped fibers or staple fibers can be released is arranged above the film 23. The nozzles 39, 40 and 41 are fixed in place. Above and across the foils 23 and 43, doctor blades 44 and 45 are arranged. The; iöhe the scraper knife over the foils is adjustable.

The film or tape > - \ 3 runs around rollers 46 and 47 and the films or o & nder 23 and 43 are together /, v / ischen and passed around columns 49, 50 and 52, respectively, with the Gaps between the rollers or the rollers 49, 50 and 52 are adjustable. Kneading rollers 48, 51 and 53 are in contact with foils 23 and 43.

The device shown in FIGS. 3 and 4 has corrugated rollers 30 and 3I with a diameter of 30.48 cm, around which a 91.44 cm wide conveyor belt 25 made of glass fiber reinforced silicone rubber runs, a conveyor bond guide device 35, 36, tensioning rollers 32, 33 and 34 , a spindle 38 and a drive motor and drive unit 37. These device parts differ only from those described above in relation to FIGS. 1 and 2.! I by the fact that the conveyor belt has no sealing cuffs or lips, on r, c .inert; -Edge soak.

309826/1046,

_ 37 -

The device shown in Figures 3 and 4 also has a second conveyor belt 56 made of silicone rubber, which runs around corrugated rollers 57 ¹¹ ^ d 58 each with a diameter of 30.48 cm, a conveyor belt guide device 59, 60, tension rollers 61, 62 and 63 and a Drive motor and gear unit 64 on.

• Furthermore, there are numerous above and in this device arranged below the conveyor belts 25 and 56 and with these in contact pressure plates 54, 55 provided by the heating or cooling liquid can be conducted as required.

To carry out Examples to 9, the container 1 was each with ethylenically unsaturated polyester, ethylenically un-. saturated monomer, polyfunctional compound, polymerization inhibitor, figment, particulate! Filler and separating agent charged, whereupon the container ^{contents stirred and heated to 40 0} G, soxtfie the container 1 was evacuated in order to remove air from the mixture contained therein. The container 2 was charged with polyisocyanate and polymerization catalyst, whereupon its contents were treated analogously to that of the container 1. In the manner described with reference to FIGS. 1 and 2, the contents of the containers 1 and 2 were then circulated and pumped to the mixing head or mixer 15 at the desired speed, whereupon the mixed flows (pre-product mixture) from the nozzles 39 and 40, respectively Chopped up gas fibers were applied to the film or tape 23 ^{from the nozzle L} \ '\. The height of doctor blades 45 and 44 were respectively

3 09 826/10 46

accordingly, the desired thickness of the layer of the mixture the foils or tapes 23 and 43 are set.

The foils 23 and 43 and the conveyor belt 25 were driven at the desired speed and a sandwich of the mixture of resin, fibers and filler was formed between the foils 23 and 43. The films were then passed around the rollers 49, 50 and 52, whereupon the mixture trapped between the films was kneaded by the kneading rollers 48, 51 and 53. The foils 23 and 43 were then passed between the printing plates 54, 55 by means of the conveyor belts 25 and 56, the printing plates being heated with steam or cooled with water in such a way that the foils 23 and 43 and the mixture enclosed between them initially heated along a distance of 609.6 cm to 70 ⁰ C and. The last 121.92 cm were then cooled to 20 ° C., then the non-sticky, flexible, pliable plate produced in this way, lying between the foils 23 and 43, was wound onto the spindle 38 and until it was used up stored for the production of moldings.

To produce moldings V7, the polyethylene films 23 and 43 were removed from the flexible, pliable, non-adhesive plate removed, whereupon it is used to create the pile of a dimensionally stable body was molded and heated.

Example 6

“A non-sticky, flexible, pliable sheet evolved Using 36 percent by weight of polyurethane precursors and 64 percent by weight of precursors for cured polyester resin

309826/1048

the following starting materials and using the following Pump speeds established:

Atkylenically unsaturated polyester 21.62 kg; (as in example 1)

ethylenically unsaturated monomer 13.22 kg; (Styrene)

polyfunctional compound (propoxylating

tes bisphenol-A) (as in Example 1) 11.89 kg;

Inhibitor (triethylene glycol-hydroquinone mixture in a weight ratio of 2: 1)

Pigment (Scott Bader and Co. Ltd., 199 yellow)

Filler (Millicarb calcium carbonate) Release agent (zinc stearate). Polyisocyanate C as in example 2)

Polymerization catalyst (tert-butyl peroctoate) 0.586 kg;

Glass fibers, chopped (Silenka Type 871S)

Pump speed container 1 3.5 kg / minute

Container 2 0.181 kg / minute.

The running speed of the foils 23 and '+3 and the conveyor belts 25 and 56 was 12.1.92 cm / minute. The thickness of the Geraischschicht between foils 23 and 4-3 was 2.03 mm. The one with it

O , 161 kg; 1 , 34- kg; 75 kg; 1 , 93 kg; 7th 5 5 kg;

preserved, 91.44 cm wide, non-sticky, flexible, forged

2
This plate contained 7.5 g of glass fibers per dm, corresponding to a glass fiber content of 20 percent by weight.

This plate could easily be stretched and shaped into various shapes.

309 8 267 VoW

A stack of ten square samples of the plate with an edge length of 27.1 ^ cm was formed into a chair with a backrest and four tapered legs by compression molding and heating at 125 ° C. for 5 minutes under a pressure of 10.55 kg / cm .

A sample of the flexible, The flexible plate was slit and torn apart into two layers of roughly equal thickness. The fiberglass in the layers appeared to have been wetted by the resin, since no or only a few unwetted white strands could be seen in the resin was.

en lhieil
In contrast to this / a flexible, pliable plate produced in an analogous manner, the production of which has only deviated from the method described above in that the foils 25 and Ό and the mixture in between are not heated during the passage between the pressure plates 54 and 55 became; a significant proportion of fibers that had not been wetted by the resin and were therefore white and easily seen in the panel,

Example 7

Example 6 was repeated, notwithstanding this, only the nichtklcbrdgo, flexible, supple plate ov & ^ S Gowichtsprozcnt Polyurotbanvorprodukton and 65 percent by weight of raw materials for cured polyester resin under Verv / sing the following "Ausgongsmaterdalien and the pumping rates given below produced v / urde:

309826/1046

Ethylenically unsaturated polyester 3.76 kg;

(as in example 1)

ethylenically unsaturated monomer 2.33 kg;

(Styrene)

polyfunctional compound (propoxylating

tes bisphenol-A) (as in Example 1) 2.08 kg; Pigment (Scott Bader and Co. Ltd .;

red pigment) 0.22 kg;

Filler (calcium carbonate; Omya) 10.1 kg;
Release agent (zinc stearate) 0.4 kg;

Polyisocyanate (as in Example 2) 1.14 kg; Polymerization catalyst (tert-butyl perbenzoate) . 0.089 kg;

Glass fibers, chopped (Type FGRE 11; Fiber Glass Ltd.);

Pump speed '' container 1 1.51 kg / minute "" container 2 0.083 kg / minute.

The running speed of the foils 23, 43 and the belt 25 was 60.96 cn / min. The density of the mixture between the foils 23 was 2.03 mm. The 91.44 cm wide, non-sticky, flexible, pliable sheet obtained contained 7.54 g of glass fibers per dm ", corresponding to a glass fiber content of 20% by weight .

jJine j; .obe of the resulting plate was made by compression molding and heating at 135 ° C for 10 minutes under a pressure of

10.55 kp / cm to a rigid, dimensionally stable box with exncjr square base (edge length 4 5.72 cm) and 45.72 cm high walls processed.

309826/10 46

Example 8

From the starting materials given in Example 7 , a further, non-sticky, flexible, pliable plate was produced which, however, differed from the one obtained in Example 7, contained 32 percent by weight of glass.

A sample of this plate was analogous to Example 7 to a rigid, dimensionally stable, closed on one side, 45.72 cm long cylinder

309826/1046

linder processed with an inner diameter of 45.72 cm.

Example 9

Another, non-sticky, flexible, pliable sheet was produced from the starting materials described in Example 7 ', where, however, differently as calcium carbonate

and

Microdol Xtra filler / two glass fiber mats instead of glass fibers (SuprEmat, Fiber Glass Ltd.) Uses vmrdo (n), the between the foils 23 and 43 were fed. The plate obtained in this way contained 20% by weight of glass fibers.

A sample of the plate was compression molded for 15 minutes 125 ° G and under a pressure of 10.55 kp / cm to a rigid, Dimensionally stable box as described in Example 7 processed.

In the following examples 10 to 12, analogous to that in the procedure used in Examples 6 to 9, formable laminates made of one or both sides with one or two polymer material layer (s) laminated or laminated, non-sticky, flexible, pliable plate made of a mixture of i'olyui'ethsnvorprodukte and the precursors of a hardened polyester resin produced, but notwithstanding this, if the laminate had a polymer layer, the lower polyethylene film 23 and, if the laminate had two layers of polymer material, both polyethylene films 23 and 43 by one layer; made of polymer material (s).

309 82: 6/10

Example 10

To produce a laminate with two polymer material layers th and an intermediate, non-sticky, flexible, pliable plate, Example 6 was repeated, with a difference of which the two polyethylene films 23 and 43 "respectively by a 0.254 mm thick film or layer made of a polyvinyl chloride-ABS mixture (Vulkide 05; Imperial Chemical Industries Limited) were replaced.

Laminot

The resulting / easily converted into a variety of different Form molded body.

A sample of the laminate was formed by vacuum forming ¹ at a temperature of 125 ° C and held on the mold of the vacuum forming device to form a trough with the base dimensions 4-5 * 72 x 30.48 cm and at an angle of 45 to create walls that are 10.16 cm high and inclined towards the base.

Example 11

Example 10 was repeated, but comparing it instead of the foils or layers made of a polyvinyl chloride-ABS mixture two 0.0762 mm thick foils bsw. Layers of one Acrylic resin (Korad, Lennig Chemicals) were used.

The laminate obtained in this way could easily be shaped into a large number of different shaped bodies.

A sample of the laminate became a trough analogously to Example 10

309826/1046

or a tub processed, with a 5-minute curing at 125 0 was applied.

Example 12

Example 10 was repeated, but differing therefrom from the two polyethylene foils 23 and 4-3 only one, namely the lower one Polyethylene film 23 replaced and in its place instead of the film or layer of polyvinyl chloride-ABS mixture 0.3048 mm thick film or layer of plasticized polyvinyl chloride (Novan 712; Imperial Chemical Industries Ltd.) is used became.

The laminate obtained was after removing the polyethylene film 23 processed into a tub analogously to Example 10, wherein the laminate was placed in the mold in such a way that the sheet or layer of plasticized polyvinyl chloride was in contact with the mold. '

Patent claims :

309826/1046

Claims (1)

Claims 1. ^ Process for the production of further deformable moldings Polymer material through partial conversion of a mixture of precursors or starting materials for the polymer material from, based on the weight of the preliminary products, a) 5 to 95 percent by weight of the precursor of my polyurethane at least one polyfunctional compound with at least two groups capable of reacting with isocyanate groups and at least one polyisocyanate b) 95 to 5 percent by weight of precursors of a cured polyester resin of at least one ethylenically unsaturated polyester and at least one copolymerizable therewith, ethylenically unsaturated monomer, characterized by the Flowable mixture of the precursors gives up on a moving carrier surface and in contact with this so largely converts or lets react that a manageable shaped body is formed which can be further deformed. 2. The method according to claim 1, characterized in that a belt or conveyor belt is used as the carrier surface J. Process according to Claim 1 or 2, characterized in that a plate or film is produced as the further deformable shaped body. 4. The method according to any one of claims 1 to 3, characterized 309826/1046 draws that polyurethane precursors are used, which are im are essentially free of ethylenic double bonds. 5 · Method according to one of the preceding claims, characterized characterized in that at least one ethylenically unsaturated polyester with at least two isocyanate groups as the starting material reactive groups in the molecule is used. 6. The method according to any one of the preceding claims, characterized in that the Polyurethanvorprodulcte each other and, if an ethylenically unsaturated polyester containing isocyanate-reactive groups is used, with the ethylenically unsaturated polyester essentially completely implemented, and that the process is carried out in such a way that essentially no interpolymerization between the ethylenic unsaturated polyester and the ethylenically unsaturated monomer takes place. 7. The method according to any one of the preceding claims, characterized characterized in that the mixture of precursors on the carrier surface is reacted by heating. 8. The method according to claim 7 »characterized in that the mixture of preliminary products on the carrier surface is heated ^{to a temperature of at least 50 ° C.} 9. The method according to any one of the preceding claims, characterized in that the mixture of precursors on the carrier 309826 / 1ΟΛΘ ^: '^ " surface contains a particulate material. 10. The method according to claim 9, characterized in that the mixture of precursors on the carrier surface, based on the total weight of the mixture of particulate material and the precursors, contains up to 70 percent by weight of particulate material. 11. The method according to any one of the preceding claims, characterized characterized in that the mixture of precursors on the carrier surface contains a fiber material. 12. The method according to claim 11, characterized in that the mixture of preliminary products on the '!' Räf- ^ poberf] äci. · '. i «r" crcn- »uf the gene, weight of the fiber material and the mixture of precursors, contains up to 70% by weight of fiber material. . 13-, predecessors to ο j rom dor vorhorrehonden claim; ", characterized in that Daii dr; s mixture dor precursors on the substrate surface, based on the Gesrintt ^'r -" vel ^v!' 'Of the particles' ürnn gen Ilaterials and! of the preliminary product mixture contains up to 60% by weight of toilet- shaped material and, based on the total weight of the fiber material and the preliminary product mixture, up to 50% by weight of fiber material. Λ '\. Method according to claim 13, characterized in that d-τί? a mixture of the preliminary products on the carrier surface, based on the total weight of the particulate material and the preliminary product, 10 to 60 wt. 309826/1046 _B ad original rial and, based on dfis Gcnnnt;. ~ cv7Jchü of the fiber material and The intermediate product is a mixture of up to 50% by weight of fiber material holds. 15. Method according to one of claims 11 to "14-, characterized in that that glass fibers are used as fiber material. 16. The method according to any one of claims 11 to 15, characterized in that ds3 the possibly a partial material containing mixture of the preliminary products on two Tr-'jgerobei'flächen abandoned, the fiber material with the mixture of precursors on one or both carrier surfaces in contact brought and the .the resulting mixtures supporting Tri'gcroberflächen combined so that they optionally contain a particulate material mixture of the Pre-products and the "fiber material like a sandwich core layer to enclose between them. 17. The method according to any one of claims 1 to 16, characterized in that that a mixture of precursors is used, the 30 to 70 percent by weight of polyurethane precursors and 70 to 30 percent by weight of precursors of a hardened polyester resin contains. 18. The method according to any one of claims 1 to 17 _? characterized in that a laminate with a layer of a moldable polymer material is produced as the further deformable molded body. · 309 826/1046 19 · Method according to claim 18, characterized in that a laminate is produced as a further deformable standard body, which has a layer of a moldable polymer material as a cover layer on both sides of the core layer. 309826/1048 Si Blank