SE407418B - MOLDING COMPOSITION FOR THE MANUFACTURE OF PLASTIC ARTICLES, FORMED FROM A MIXTURE CONTAINING POLYURETHANE PRECURSORS AND PURYCURED POLYESTER HARD PRECURSORS - Google Patents

Description

__ ____.__...._...___-__._._..._ í .__ s ...___.__ i_.i_.i..ï_íí .__ '7302511-6 to a rigid product by copolymerization of the ethylenically unsaturated the monomers with the ethylenically unsaturated groups in the polyester. Although the single profile moldable article can be surface shaped further before it is finally put into use, e.g. by vacuum forming molding or draping over a mold, however, it has shown that difficulties may arise in shaping the object in disturbance. extent, and as an example, that it can be difficult to deep-draw the object by vacuum forming. In a similar way can it, when the object with a simple profile is molded, can be difficult to get material in the object to float to the required extent when a finished product with a very complicated form is desired. The difficulties encountered da in terms of making the object float to a greater extent, be able have their cause in the presence of the object of a bridged network, automobile by reacting the polyfunctional compound, the polyisocyanate and the ethylenically unsaturated polyester.

It has now been found that a molding composition which can made of a shaped object with a simple profile, which is in possession of Desirable forming properties, can be formed from a mixture of precursors. to a crosslinked polyurethane and precursors to a cured one polyester resin by ensuring that the proportion of polyfunctional tional compound and ethylenically unsaturated polyester relative to polyisocyanate in the mixture of precursors is within a careful range selected area. The molding composition of the present invention is generally more malleable than the composition described herein. also in the above-mentioned British patent specification. In particular, the composition can according to the present invention is more easily formed into the present invention. goals with complicated profile and it is generally possible, in such cases where the composition is formed by compression molding, to apply pressure which are lower than, and often considerably lower than, the pressures required to form the composition, which is described in the British the patent in question. ' Furthermore, the composition of the present invention is further generally neither too stiff nor too stiff because it does not easily should be able to be formed, but it is also, in general, not so flexible. bel, that it is sticky and uncomfortable to handle.

According to the above-mentioned British patent specification, the objects are formed with a simple profile from a mixture of precursors to a cross-linked lyurethane and precursors to a cured polyester resin, where the between isocyanate-reactive groups in the polyfunctional compound gene and ethylenically saturated polyester to isocyanate groups in polyisocyanate 7302511-6 the moisture content is preferably substantially 1: 1, and in all conditions in generally the inememraaet is o, a = 1 - 1.1 = 1.

It has now quite surprisingly turned out, that in the compositions according to the present invention the ratio of isocyanate-reactive groups per in the polyfunctional compound and ethylenically unsaturated polyester to isocyanate groups in the polyisocyanate generally lies considerably outside the areas set out in the British patent specification in question and hitherto considered necessary in the field of polyurethane chemistry.

In accordance with the present invention, there is provided a molding composition for the manufacture of plastic articles, formed from a mixture containing _ (a) 5-95% by weight of precursors to a polyurethane, containing at least one polyfunctional compound, which contains groups which are reactive towards isocyanate groups, and at least one poly- isocyanate, the functionalities of the polyfunctional compounds being and for the polyisocyanates are in the range 2-5, preferably in the range 2-4, and the functionalities of at least one of the polyfunction the active compounds and / or at least one of the polyisocyanates are highly re than 2, and (b) 95-5% by weight of precursors to a cured polyester resin, containing at least one ethylenically unsaturated polyester and at least one ethylenically unsaturated monomer which is copolymerizable with the ethylenically unsaturated the groups in the polyester, wherein the polyfunctional compound and the polyisocyanate is reacted together with the ethylenically unsaturated the polyester, in which case the polyester contains isocyanate-reactive groups, to an extent such that a manageable, malleable composition formation, the proportions of polyfunctional compound, poly- isocyanate and ethylenically unsaturated polyester in the mixture are selected so that either (l) the number of moles of isocyanate-reactive groups in the polyfunctional la compound plus the ethylenically unsaturated polyester, in such cases then the polyester contains isocyanate-reactive groups, is greater than the number moles of isocyate groups in the polyisocyanate and the ratio Y, ie 1/2 (u-1), where number of moles of isocyanate-reactive groups in the functional compound plus ethylenically unsaturated a = polyester number of moles of isocyanate groups is in the range X - 0.15 to X + 0.15, or (2) the number of moles of isocyanate groups in the polyisocyanate is greater than the number of moles of isocyanate-reactive groups in the polyfunctional plus the ethylenically unsaturated polyester, in those cases where the az1> §sa11a i 4 the lyester contains isocyanate-reactive groups, and the ratio Z, ie 1/2 (à - 1), is in the range X - 0.15 to X + 0.15, where the average functionality of the average functionality of the the polyisocyanates - 2 functional compounds, reactive X = '' _ + tiva with isocyanate - 2. , 2 2 Although it is not necessary that the ethylenically unsaturated poly- the ester contains groups which are reactive with the isocyanate However, it is preferable that the polyester contain such groups, and by way of example, the polyester may contain in each molecule has at least two such groups.

Preferably, the polyurethane precursors are substantially free of ethnic unsaturation. it is desirable that the mixture from which the molding composition is produced, is homogeneous, ie does not contain any excessive excretion visible to the naked eye, even if in accordance with the purposes of the finding do not preclude the presence of a certain turbidity in the mixture.

The molding composition is formed by reacting the polyfunctional the national compound and the polyisocyanate together with the ethereal polyunsaturated polyester, in cases where the polyester contains iso- cyanate reactive groups, the extent of the reaction being selected as follows, that a molding composition with the desired consistency is formed. Reactive shall be carried out to such an extent that a manageable, bar composition is formed, i.e. a composition which can be easily formed but which is not so sticky that it can not be handled comfortably. Fö- year-round, the composition is non-sticky. Intended to produce a such an easily manageable and malleable composition, the above-mentioned reaction is suitably carried out substantially completely, ie in such cases when the polyisocyanate is present in excess, such groups in the lyphunctional compound and the ethylenically unsaturated polyester, which are able to react with the polyisocyanate, should preferably have reacted to this to a considerable extent. In a similar way, i such cases where the polyfunctional compound and the ethylenically unsaturated the polyester are present in excess, that the polyisocyanate generally reacts substantially completely with such groups in it the polyfunctional compound and the polyester, which are capable of reacting with the polyisocyanate. Control of the reaction of the polyisocyanate with the polyfunctional compound and optionally with the ethylene unsaturated polyester will be discussed in more detail below.

It is preferred that in the molding composition the ethereal '7302511-6 5 non-polyunsaturated monomer and ethylenically unsaturated polyester are copolymerized to a more significant extent, although a some copolymerization may take place, provided that it does not has any detrimental effect on the kdmxßithmrms fi nmbæ fl æt.

The molding composition, which may conveniently be in the form of a sheet or foil, can, if desired, be formed into an article and more complicated profile and the curing reaction, thereby in the present case refers to the copolymerization of the ethylenically unsaturated polyester and the ethylenically unsaturated monomer in the composition, can be carried out to give a hardened article; With functionality of the polyfunctional compounds, reactive in association with isocyanate, and functionality of polyisocyanate in this context, the average number of groups per reactive to isocyanate groups per molecule polyfunctional compound resp. the average number of isocyanate groups per per molecule of polyisocyanate. In such cases e.g. then the polyisocyanate contains a mixture of compounds with different functionality, can the average functionality of the polyisocyanate in the mixture is calculated by conducting the molar proportions of the isocyanates in the mixture and the functionality of each isocyanate. So e.g. is, in a mixture of 1 mole of triisocyanate and 1 mole of a diisocyanate, average functional of the polyisocyanate in the mixture thereof 2.5. Similarly, in a mixture of 2 moles of a triisocyanate and 1 mole of a diisocyanate nat, the average functionality of the polyisocyanate in the mixture thereof is 2.67.

Because the functionality of at least one of the polyfunctional the compounds and / or polyisocyanates are at least two, are polyurethane the precursors such that they are capable of forming a crosslinked poly- urethane.

By number of moles of isocyanate groups in the present case is meant the total speak the number of moles of isocyanate groups in the polyisocyanates in the mixture.

So e.g. there is, in 1 mole of a triisocyanate, 3 moles of isocyanate groups, and in a mixture of 1 mole of a diisocyanate and 1 mole of a triisocyanate there are 5 moles of isocyanate groups.

When in the present case isocyanate-reactive groups are mentioned, or groups which are reactive together with isocyanate, are meant groups in the polyfunctional compound, and optionally in the ethylenically unsaturated those polyesters which are capable of reacting with isocyanate and which are not react with the isocyanate under the conditions used in the preparation the position of the molding composition. The polyfunctional compound must contain such isocyanate-reactive groups and have a functionality r v _fïnom area 2-5. '- "f 7zo2s11-6 is So e.g. are, in cases where the polyfunctional The compound contains hydroxyl groups, e.g. when the polyfunctional The compound is a polyester or polyether polyol, such groups known to react readily with isocyanate groups, t.o.m. vid omgi i V even temperature, and thus come, in such cases as forming comp fi šï the reaction is prepared by reacting at ambient temperature, the xyl groups in the polyester or polyether polyol to be isocyanate-I reactive groups. Similarly, in cases where the The polyunsaturated polyester contains hydroxyl groups, these hydroxyl groups to react with the polyisocyanate, t.o.m. at the ambient temperature temperature, and are thus isocyanate-reactive groups. On the other hand the ethylenically unsaturated polyester can e.g. contain carboxyl groups, which, although capable of reacting with isocyanate groups, in particular at elevated temperatures, are known to be much less reactive. relative to isocyanate groups than is the case, for example with hydroxyl groups, especially at ambient temperature. In such cases where the polyester contains such carboxyl groups, these are considered isocyanate-reactive groups only in those cases where they react with the polyisocyanate under the conditions used in the preparation of the molding composition. So e.g. it has been shown that in such cases where the molding composition is prepared from a mixture, containing an ethylenically unsaturated polyester, which in turn contains both hydroxyl groups and carboxyl groups, if the composition is prepared read at ambient temperature or at a temperature 1 nearby hence, only the hydroxyl groups react within the time required to form the molding composition, and thus only the hydroxyl groups, but not the carboxyl groups, are considered to be iso- cyanate-reactive groups. On the other hand, if the molding composition ' prepared at elevated temperature, the carboxyl groups may react with the polyisocyanate and if that really happens, they should also be considered be isocyanate-reactive groups. Whether the groups that are able_ to react with the polyisocyanate, really react or not during the conditions used in the preparation of molding compositions. can be easily determined by simple experiments. So e.g. can, in cases where the ethylenically unsaturated polyester contains both hydroxyl and carboxyl groups and the molding composition is formed at at ambient temperature, a mixture of the polyester and the isocyanate used in the preparation of the molding composition, stored at ambient temperature for the same period of time as used in the preparation of the molding composition, and the mixture UALITy 7302511-6 can be analyzed, e.g. using infrared spectroscopy, for determination of whether the carboxyl groups in the polyester reacted with the polyisocyanate or not.

In order that the molding composition of the present invention shall be particularly well suited for further shaping, and in particular _ so that the composition can flow very easily, so that the products with a complicated shape can easily be produced, lie retrograde conditions for Y or Z, as is now the case, within the range X - 0.4 to X + 0.4.

The properties of the cured article, prepared from molding the composition by copolymerization of the ethylenically unsaturated mono- with the ethylenically unsaturated polyester, are dependent on the between polyurethane precursors and cured polyester resin precursors in the mixture from which the molding composition is prepared read, and it is to lecture, for the hardened article to may have a good combination of properties, that the mixture, from which the molding composition is prepared contains 40-50% by weight. percent, preferably 20-40 weight percent, polyurethane precursors and 90-50% by weight, preferably 80-60% by weight, cured polyester resin precursors.

Conveniently, the functionality of both the polyfunctional the purification and the polyisocyanate are between 2 and 5, at least either of the polyfunctional compound and the polyisocyanate has one functionality higher than 2. f Groups in the polyfunctional association, which are able to react with isocyanate groups, include e.g. -NH2-, -OH- and -COOH- groups, and in the ethylenically unsaturated polyester include suitable such groups are -COOH and -OH groups, although, as is clear from on the basis of the above discussion, in such cases where the polyester (or the polyfunctional compound) contains carboxyl groups, these groups can react under the conditions used in position of the molding composition, only about the molding composition produced at elevated temperature.

In order to further elucidate the invention, one will now follow illustrative calculation, showing how the amount of polyisooyanate, which shall be used in conjunction with the given amounts of cured polyester resin precursors and polyfunctional compound, can be calculated to give a mixture from which a molding composition within the framework of the present invention can be made. 7302511-6 Hardened polyester resin precursors 20 g of ethylenically unsaturated monomer 20 g of linear, ethylenically unsaturated polyester having a molecular weight of 4000 and containing hydroxyl end groups.

Number of moles of ethylenically unsaturated polyester = 0.005 mol.

E Number of moles of isocyanate-reactive (hydroxyl) groups in the ethylene unsaturated polyester = 0.01 mol (ie two such groups per molecule).

Polzurethane precursors 40 g of diol with a molecular weight of 400 Number of mol aioi = 0.1 mol I Number of moles of isocyanate-reactive (hydroxyl) groups in the diol = 0.2 mol. second order transition for triisocyanate with a molecular weight of 300 Functionality of the triisocyanate = 3 and functionality of diols: 2. _ 3 - 2 _ x _ 2 "opsu Total number of moles of isocyanate-reactive groups = 0.21. (l) In the case where the isocyanate-reactive groups in the poly- the functional compound plus ethylenically unsaturated polyester are present in excess of the isocyanate groups in the polyiso- the cyanate, the ratio Y is obtained by means of the equation 0.21. _ 1) number of moles of isocyanate groups 1/2 ( 0.15 = 0.5 É 0.15, of 0.35 to 0.65, preferably 0.1 = 0.5 3 0.1, off 0.4 to 0.6.

H- 1 + Thus, the number of moles of isocyanate groups required is the same with 0.124 ~ 0.09l3, preferably 0.117 - 0.0955.

Since the polyisocyanate used is a triisocyanate, it is number of moles of triisocyanate required 0.04l3 - 0.0304, preferably 0.039 - 0.0318, and since the molecular weight of the triisocyanate is 300 12.39 - 9.12 g of triisocyanate, preferably 11.7 - 9.55 g, be used. _ It should be noted that in the above illustration the molar ratio between isocyanate-reactive group fi and isocyanate groups in the mixture is in the range 1: 0.59 to 1: 0.435, preferably in the range 1: 0.557 to 1: 0.454, ie it differs considerably from the ratio of about 1: 1, which has hitherto been considered necessary. J '7302511-6 79 '- - = - __________ l _- ._, n, ____ ___ (2) In the case where the isocyanate groups in the polyisocyanate are present in excess relative to the isocyanate-reactive groups in the ethylenically unsaturated polyester plus the polyfunctional compound, the ratio Z is obtained by the equation % (Number of moles of isoolanate groups _ 1) 0.21 z = x + 0.15 = 0.50 in 0.15, i.e. 0.55 to 0.65, preferably z = X i 0.1 - 0.50 1 0.1, ie 0.40 to 0.60. ' Thus, the number of moles of isocyanate groups required is the same with 0.557 - 0.485, preferably 0, 578 - 0.462. _ Since the polyisocyanate is a triisocyanate, it is the number of moles triisocyanate required 0.119 - 0.161, preferably 0.126 - 0.154, and since the molecular weight of the triisocyanate is 500, 55,? - 48.5g _ triisooyanate, preferably 57.8-46.2, can be used.

It should be noted that in the above illustration, the relationship between isooyanate reactive groups and isooyanate groups in the mixture 5 is in the range 1: 1.7O to 1: 2.50, preferably 1: 1.8Ö to 1: 2.20, ie it differs most significantly from the ratio, as hitherto believed to be necessary.

Suitable polyfunctional compounds include e.g. polyols, such as polyether polyols, and polyesters, in particular mainly hydroxy -finished polyesters.

Examples of suitable polyols include glycols with the structure HO-R-OH, where R is e.g. an alkylene chain such as ethylene glycol, propylene glycol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, di (ethylene) carbon) and di (propylene glycol). Other suitable polyols include poly- merers, preferably those of low molecular weight, obtained from glycosides clay, e.g. poly (ethylene glycol), poly (propylene glycol) and poly (butylene glycol). glycol). Suitable polyols which are trifunctional or which have now higher functionality, include e.g. glyoerol, pentaerythritol, neopentyl glycol, trialkylol alkanes such as trimethylolpropane, triethylol propane, tributylolpropane, and oxyalkylated derivatives of said tri- alkylol alkanes, especially those of low molecular weight, such as oxyethylene trimethylolpropane and oxypropylated trimethylolpropane. Oxialkylera- the glyoerols are also suitable, e.g. oxypropylated derivatives of eg glycerol, especially such low molecular weight derivatives.

Examples of suitable polyesters include condensates of at least one diol having the structure HO-R-OH, with at least one dicarboxylic acid having the structure pure HOOC-R-COOH, where R is e.g. an alkylene chain, which may be the same ¿A; 7zo2s11-e Ho? a a_ I e- or different in the diol and in the diacid. Suitable examples include poly (ethylene adipate), poly (ethylene sebacate), poly (ethylene glutarate), poly- (ethylene pimelate), poly (propylene adipate), poly (propylene sebacate), poly- (propylene glutarate) and poly (propylene pimelate).

Suitable polyesters with a functionality higher than 2 can be produced by condensation of one or more polyols with a functional higher than 2, optionally in admixture with one or more diols, with one or more dicarboxylic acids. If desired; can an electric several of the dicarboxylic acids are replaced by one or more carboxylic acids. acids with a fmmtienaiitet higher than 2. Alternatively, one or several polycarboxylic acids with a functionality higher than 2, optionally in admixture with one or more dicarboxylic acids, condensed with one or more diols. Polyesters with a functionality higher than 2, which can be prepared, include in particular a condensate of adipine acid with glycerol and either ethylene glycol or propylene glycol, and a condensate of adipic acid with trimethylolpropane and either di (ethyl 'long glycol) or propylene glycol.

Due to the desirable properties of those obtained therefrom products, and in particular with a view to achieving an optimal balance between impact strength and wear resistance temperature, such urethane precursors to be preferred, which, if cured alone in the cured polyester resin precursors, give a crosslinked polyurethane with a glass / rubber transition temperature of not less than 25 ° C, preferably at least 5500. A professional in the field of polyurethane chemistry and technology easily realize how the choice of polyurethane precursors, which meet this requirements, shall be made.

In order that the cured article, which is prepared from molding compositions, according to the present invention, will have a good combination of properties, and in particular a good combination of impact resistance e strength, bending properties and thermal properties, it is preferable, in such cases where the molding composition is prepared from polyurethane precursors, containing a difunctional compound, and a polyiso- cyanate with a functionality in the range 2-5, that the difunctional the compound yields an average of no more than 55 chain atoms in the macromolecular learn the chains in the composition.

By "in-chain atoms" in the present context is meant atoms or groups, which form part of the macromolecular chains in the composition, and with the exclusion of atoms or groups hanging from the chain jan, and which, in the event that the macromolecular chains contain a cyclic group, the number of in-chain atoms is determined by the shortest the distance around each ring.

Diols, containing aromatic groups, can also be used, e.g. diols with the structure ' 7302511-6 14 f ' where B is a direct bond or a divalent group, e.g. -S02-, -O- or 34 oä- 1 R2 n where n is an integer, preferably having the value 1-4, and R 1 and R 2 are selected blend hydrogen atoms and hydrocarbyl group br, in particular alkyl groups, e.g. methyl.

Due to the desirable properties of the cured products, which are prepared from the molding composition are particularly preferred diols oxyalkylated derivatives of the diols of structure I, ie diols with the structure H ç o-eH-çH än o- Ö-B-Q-o 4: Ii-eu - o èdm H 'II; a 115 114 3 124 9 wherein R5 and R4 are selected from hydrogen atoms and hydrocarbyl groups, respectively preferably alkyl groups, e.g. methyl. '.

The sum n + m is preferably such that the units in the resultant the forming composition obtained from the diol to give a averages of not more than 55 i-chain atoms in the macromolecular chains hence.

A preferred diol of structure II is an oxyalkylated derivative of 2,2'-bis- (p-hydroxyphenyl) -propane, i.e. a diol of structure II, in which B is' CH5 and in which n + m is preferably not greater than 8 and in particular is in the range 2-4. Particularly preferred is an oxypropylated; derivatives in which either or both of R; and R 4 is H and the other E is -CH5 And n + m is an integer with a value of not more than 8, preferably with a value in the range 2-4. Suitably n and m are both '; integers with a value of 1 or 2. Ä-e'R302511'6 :, _ _ v 42- »_e ~ ef ~ - ~ - ~~» e r If desired, one or both of the aromatic groups may in the diol with structures I and II be completely saturated.

The polyisocyanate component of the polyurethane precursors may be for example an aliphatic "polyisocyanate", an aromatic polyisocyanate or a cycloaliphatic polyisocyanate, or may in the polyisocyanate contain at least two different types of isocyanate groups, selected from phatic, ¿cycloaliphatic and aromatic isocyanate groups.

As an example of the polyisocyanate component of polyurethane precursor 4,4'-dicyclohexylmethane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, xylylene diisocyanate, 2,4-toluene diisocyanate, -2,6-toluene diisocyanate or a mixture of such toluene diisocyanates. 4 In such a hell then approached proaumér with high striking needle fastness and good bending properties are desired, a preferred polyisocyanate is one with the structure NCO_ NCO 'ï B ï where B-is a divalent group. B can be e.g. -O-, -SO2- or a group with the structure 31 R2 n where n is an integer, preferably having a value of 1-5, and R1 and R 2 are selected from hydrogen atoms and hydrocarbyl groups, e.g. refrigerants, such as methyl. A preferred diisocyanate is 4,4'-diphenylmethane. diisocyanate.

As an example of a polyisocyanate with a higher functionality than 2 may be mentioned a mixture of 4,4'-diphenylmethane diisocyanate and others p polyisocyanates with a total isocyanate functionality of 2.7, as in the trade occurs as "Suprasec" DN (manufacturer IGI).

If desired, mixtures of polyfunctional compounds with functionalities in the range 2-5 and mixtures of polyisocyanates functionalities in the range 2-5, can be used, this under exposure, that the functionality of at least one of the polyfunctional the compounds and / or functionality of at least one of the polyisocyanate are higher than 2. Thus, e.g. the polyurethane precursors 7302511-6 fr; ...., __ .. a polyfunctional compound and a polyisocyanate, of which each has a functionality higher than 2, a difunctional compound and a polyisocyanate having a functionality higher than 2, a polyfunctional a compound having a functionality higher than 2 and a diisocyanate, a difunctional compound and a mixture of a diisocyanate and a polyisocyanate with a functionality higher than 2, a polyfunctional compound and a mixture of a diisocyanate and a polyisocyanate, or a mixture of a difunctional compound and a polyfunctional compound with a functionality higher than 2 and a mixture of one diisocyanate and a polyisocyanate. g e The ethylenically unsaturated polyester component is cured polyester. the resin precursors can be obtained e.g. by esterification of an immeasurable dicarboxylic acid or a mixture of such acids with a saturated diol or a mixture of such diols, or by esterification of a saturated dicarboxylic acid or a mixture of such acids with a unsaturated diol or a mixture of such diols. If desired can one or more unsaturated acids are used together with or instead for the saturated acid (s), and one or more unsaturated diols can be used together with or instead of the measuring tade diolerna. Whenever possible an anhydride can be used instead for the correspondingšäškerboxylic acid. One or more carboxylic acids with a functionality fi greater than 2 can be used with or instead of one or more of the dicarboxylic acids. Similarly one or more polyols with a functionality higher than 2 can be used together with or instead of one or more of the diols.

Examples of suitable ethylenically unsaturated polyesters include formed by esterification of maleic acid or maleic anhydride, fumaric acid or itaconic acid or mixtures thereof, with, for example, ethylene- glycol, propylene glycol, butane-4,4-diol, pentane-4,5-diol, cyclohexane-2 -1,4-diol, glycerol, trimethylolpropane or neopentyl glycol or i «Mixtures thereof. Suitable saturated acids which can also be incorporated vase in the ethylenically unsaturated polyesters described above, include for example phthalic acid or phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, glutaric acid or pimelic acid or mixed thereof. Examples of suitable ethylenically unsaturated polyesters, which may be mentioned, include in particular a condensate of isophthalic acid and fumaric acid with propylene glycol, a condensate of phthalic acid or phthalic anhydride and fumaric acid with propylene glycol, cyclohexane-1,4-diol fi or neopentyl glycol and a condensate of propylene glycol with either a fumaric acid or a mixture of phthalic acid or phthalic anhydride and. maleic acid or maleic anhydride. 'raw 0 R QUALITY 7302511-6 14 Examples of suitable ethylenically unsaturated monomers include vinyl esters, aromatic vinyl compounds and vinyl nitriles. Suitable vinyl esters include e.g. vinyl acetate and esters of acrylic acid of the formula CH 2 = CH-COORS, wherein R 5 is an alkyl, aryl, alkaryl, aralkyl or cycloalkyl group. So e.g. R 5 may be an alkyl group having 1-20 and preferably 1-10 carbon atoms. Special vinyl ester Examples that can be mentioned include e.g. methyl acrylate, ethyl acrylate, n- and isopropyl acrylates and n-, iso- and tert-butyl acrylates.

Other suitable ethylenically unsaturated monomers include e.g. esters of the formula CH2 = C (R6) COQR5, where R6 is methyl.R5 and R6 be the same or different. Special vinyl esters that can be mentioned include e.g. methyl methacrylate, ethyl methacrylate, n- and isopropyl- methacrylate and n-, iso- and tert-butyl methacrylate. in Aromatic vinyl compounds which may be mentioned include e.g. styrene and derivatives thereof, such as α-alkyl derivatives of styrene, e.g. u- omethylstyrene, as well as vinyltoluene.

Suitable vinyl nitriles include e.g. acrylonitrile and thereof, for example, methacrylonitrile.

Polyfunctional, ethylenically unsaturated monomers, ie monomers rs containing two or more ethylenically unsaturated groups, are also suitable. Suitable monomers include e.g. glycol dimethacry- 'lat, divinylbenzene and diallyl phthalate.

The mixture of polyurethane precursors and cured polyester resin precursors from which the molding composition is prepared, may contain a monofunctional isocyanate or isocyanates and / or a monofunctional compound or compounds, reactive in bond with isocyanate, the isocyanate and the isocyanate reactive the compounds are present in definite, defined proportions for the molding composition to be in possession of desirable molding properties.

Thus, in the case where the number of moles of isocyanate reactive groups in the polyfunctional compound plus monofunctional, iso- cyanate reactive compound, if present, optionally plus the ethylenically unsaturated polyester, exceeds the number of moles of isocyanate groups in the polyisocyanate, plus monofunctional isocyanate, if dant is present, the ratio Y 'be equal to 1/2 (ou-l) + we + y 7302511-6 45 '* "" i' "" "^" "" * "" "" c *** “" tvtttt- “ number of moles of isocyanate-reactive groups in the polyfunctional F compound plus the ethylenically unsaturated polyester plus monofunctional, isocyanate-reactive compound Q ' W: hrs Q s l number of moles of isocyanate groups in the polyisocyanate plus the mono- functional isocyanate. number of moles of monofunctional isocyanatreactive compound number of moles of isocyanate-reactive groups in the polyfunctional the compound plus the ethylenically unsaturated polyester plus the monofunctional, isocyanate-reactive compound number of moles of monofunctional isocyanate number of moles of isocyanate groups in the polyisocyanate plus the mono- the functional isocyanate P c Alternatively, in such cases the number of moles of isocyanate groups in the polyisocyanate, plus the monofunctional isocyanate, as such is present, exceeds the number of moles of isocyanate-reactive groups in it polyfunctional compound, plus monofunctional, isocyanate-reactive compound, if present, optionally plus the ethylenically unsaturated dë'polyester, the ratio Z 'be equal to 1 I 1 , - \ _ '% (' äI-1) + 0f-ß + 'ä: 7 Y 'and Z' are in the range X É 0.15, preferably X É 0.40, where X has the above definition. ' Suitable monofunctional compounds, reactive with isoeyanate groups, include e.g. alcohols and amines, e.g. alcoholic holes with the structure R7OH, where R? is an alkyl group, e.g. one who has 1-40 carbon atoms, or a cycloalkyl group. Other suitable monofunctional- 1 Compounds include compounds having the structure R7NH2. Equally In this way, the monofunctional isocyanate may be an isocyanate with the structure R7NCO. and É The molding composition of the present invention may also contain fibrous reinforcement material, in order to the properties of hardened articles, made from the molding composition, are to come to get improved properties and in particular improved impact resistance strength and bending properties.

The amount of fibrous material to be incorporated into the composition depends on the desired improvement in the particular property of it shaped, hardened articles, formed from the composition, which is of greatest interest. In general, an amount of 5-50%, or even 70%, fibrous material, calculated on the total weight of fibrous material and composition, sufficient. In such cases where it is desirable to provide come a significant improvement in properties is 20-50% by weight fibrous material a preferred. vzoizišäiíi-s 16 The fibrous materials can be incorporated into the composition in a manner which are well known to a person skilled in the art of reinforced resins and shoes. la mixed with the mixture of precursors before little or none reaction at all took place.

Suitable fibrous reinforcements e and carbon fibers as well as organic polymer fibers or reinforcement material included glass, asbestos- material, e.g. nylon and polyethylene terephthalate.

Glass fibers may be in any suitable form, of a carpet, tape, tape, continuous fibers or roving. When ro- wing used, it preferably has a length of at least 6 m. for example in shape The composition may also contain pigments and stabilizers, for example antioxidants, antiozonants and UV stabilizers as well as par- É tick-like reinforcement material, e.g. talc, mica, calcium carbonate, alumina and carbon black.

In cases where particulate reinforcement or reinforcement in a variety of 20-50% by weight, material is used, it can be suitably used 5-50%, or t.o.m. 70% by weight, calculated on the total weight of the particulate matter preferably the material and the composition.

The molding composition of the present invention may prepared by reacting a mixture of precursors to a polyurethane and precursors to a cured polyester resin, of type described above, optionally in the presence of at least one mono- functional isocyanate and / or at least one monofunctional, isocyanate natreactive compound, and reacts the polyfunctional compound, the polyisocyanate and the ethylenically unsaturated polyester, in such cases when the polyester contains isocyanate-reactive groups, and the mono- the functional isocyanate and / or the monofunctional isocyanate reactive compound, when present, to such an extent, that a manageable moldable composition is formed.

Suitably, the polyfunctional compound, polyisocyanate, and the ethylenically unsaturated polyester and optionally the mono- the functional isocyanate and / or the monofunctional isocyanate reactive compound is reacted substantially completely, in accordance with with what has been described above, and it is preferred that the the unsaturated monomer and the ethylenically unsaturated polyester school be substantially unpolymerized in the molding composition, wherein this latter polymerization is carried out when desired to produce a cured article from the molding composition.

In such cases when a molding composition in the form of a disc is desired 1302511-6 § w a a ». ~ _» ___._ the mixture of precursors can be introduced into a suitable form and it the desired reaction is carried out, or the reaction may be carried out race in the mixture on a substantially flat support surface, which may be e.g. a conveyor belt. in The reaction, which may take place at ambient temperature, or ' if desired at elevated temperature, eg, At a higher temperature than 5006, may be promoted by means of polyurethane catalysts » education, e.g. tertiary amines and metal salts, e.g. stannooktoat ooh aibutyitemailaurat. '¿_ The composition may contain catalysts which promote the subsequent copolymerization of the ethylenically unsaturated polyester with the ethylenically unsaturated monomer, e.g. free radical generators, suitable in a concentration of 0.5-5% by weight, e.g. peroxides, such as benzoyl peroxide, di-tert-butyl peroxide, cyclohexanone peroxide and tenabutyl tyl peroctoate, as well as photosensitizers, which are sensitive to visible light or ultraviolet light. If desired, the composition can as well contain inhibitors of free radical polymerization with the intention of reducing or prevent premature copolymerization between the ethylenically unsaturated the polyester and the ethylenically unsaturated monomer in the molding composition. sitionen. For this reason, inhibitors are particularly valuable then the polyisocyanate, the polyfunctional compound and the ethylenically unsaturated the polyester should react at elevated temperature.

The composition of the present invention may be in form of a dough-like forming composition or suitably in the form of a disc. The composition may be formed or it may be further formed. re, as the case may be, e.g. by bringing the composition 1 join the contours of a shape, e.g. using mechanical by means, or pneumatically, or by a combination thereof. Compo- the situation can be shaped e.g. by pressing between the cooperating parts in a form which, if desired, can be heated, or by draping ring over a form. A suitable method for further molding in such cases where compositions are in the form of a disc is vacuum forming in a form. In order to promote shaping, it may be desirable to heat the composition.

The product thus further formed can be removed from the mold and the curing reaction is completed, e.g. by heating in an oven, this provided that the object has the ability to maintain its form. Alternatively, and this is especially true if it is so externally the more shaped product does not have the ability to maintain its shape but outside help, the curing reaction can be completed by further ~ .. |. »....; z v »when-a. *one . Ass-u- - ». m., .s .i .w v ........... 1; 7so2s11 ~ s _48- _ heating the object while maintaining its shape using the form. ' The invention will now be elucidated in more detail by means of the following embodiment.

Example 1 The following mixture was prepared in a vessel at room temperature. namely 22.2 g of styrene, 37.8 g of an ethylenically unsaturated polyester with an acid number of 44 mg KOH / g and a hydroxyl number of 46 mg KOH / g, caused by condensation of propylene glycol, fumaric acid and isophthalic acid (molar ratio of fumaric acid to isophthalic acid = 3: 1), ie 5.07 x 10 -2 moles of isocyanate-reactive (hydroxyl) groups (carboxyl group do not react fi under the conditions used in the of the molding composition), 22.8 g of a polyisocyanate, containing 4,4'-diphenylmethane diisocyanate, and having a functionality of 2,? and a -NCO value of 409 mg KOH / g (commercially available as "Suprasec" DN, manufacturer ICI), ie 1.66 x 10 groups, 12.9 g of oxypropylated bisphenol A with a hydroxyl number of 333 mg KOH / g, i.e. 7.69 x 10 -2 moles of isocyanate-reactive (hydroxyl) group Pers and A 4.3 g of n-butyl alcohol, i.e. 5.8 x 10 -2 mol of isocyanate-reactive (OH) group Pers 0.3 g stannous octoate, Tertiary butyl peroctoate.

In the composition, in which an excess of isocyanate groups in containing isocyanate-reactive groups was used, where X = 0.55 and % (-å - 1) + a ß + å 7 = 0.35, i.e. in the range X 3 0.15 according to the present invention.

The mixture was degassed by connecting the vessel to a vacuum source and then poured into a mold to form a disc with a thickness of 3 mm, after which the mixture was allowed to stand for 24 hours at room 3 temperature, during which time the polyisocyanate reacted with the propylated bisphenol A, n-butyl alcohol and the ethylenically unsaturated polyester. 3 After 24 hours, a flexible, non-sticky, malleable disc was removed from fdrmen. Pieces were excised from the disc and transferred to another form and heated under a pressure of 7 kp / cm 2 at a temperature of 130 ° C for 15 minutes to give a stiff, cohesive disc with the following characteristics. 3 Böjmoaui 5.6 GN / mz ' ßöjnålifastnet 7o rdr / mg '7302511-6 E 19 - - ~~~ - ~. ~. 9 ~ - 2 7 ---- «- ~; Example 2, The procedure described in Example 1 was repeated, except 715 g of the polyisocyanate (ie 1.092 x 10 -1 mol of isocyanate groups), 25 g of oxypropylated bisphenol A (ie 1.48? X 10'q mol of isocyanate reaction) (OH) groups) and 0.15 g of stannous octoate were used, the alcohol was omitted, and 100 g of ground calcite (Omya BLR 5, Plastichem Ltd.) was added. _ The mixture was spread on a fiberglass mat_ (SuprEmat, Fiberglass _ Ltd) and the carpet thus impregnated was passed through the pinch between a pair of rollers. The impregnated carpet contained 20 weight percent glass fibers. _ The carpet was left untouched for 24 hours, during which ten p0ly1so_ the oyanate reacted with the ethylenically unsaturated polyester and the oxy propylated bisphenol A. - The resulting mat was non-sticky, flexible and malleable and heated in a mold under a pressure of 14 kp / omg and at a temperature of 150 ° C for 15 minutes to give a stiff, cohesive spirit disc. In the composition, in which an excess of isooyanate reaction- Ü active groups relative to isocyanate groups were used, var s (m _ 1) = 0.515 and x = 0.55, given within the range X i 0, 15 according to present invention. 9 ¿ For the sake of comparison, the experiment described in Example 1 was repeated. except that 22.8 g of styrene, 57.2 g of ethylenically unsaturated I polyester (ie 5.02 X 10-2 moles of isocyanate-reactive (hydroxyl) groups), 20.2 g of oxypropylated bisphenol A (ie 1.20 x 10 "1 mol of isocyanate reaction) active groups), 19.8 g of polyisocyanate (i.e. 1.45 x 10 groups) was used and the n-butyl alcohol was omitted. in The mixture was allowed to stand in a mold for 24 hours at room temperature.

The slice removed from the mold was cut into pieces, inserted into one mold and compression molded at a temperature of 150 ° C for 15 minutes at a pressure of 7 kp / omg in a manner similar to that described in Example r 1. The disc taken from the mold was marked by weak areas where § the pieces had not flowed sufficiently during the compression molding. 1 In this latter composition, in which an excess of iso- cyanate reactive groups in relation to isooyanet groups were used, var% (9 - 1) = 0.019 and X = 0.55. 5 thus, a (c - 1) was outside the range X in 0.15 of the present invention invention. w l-'wš v U mmm. ».......... ',. ::. ~ ~ '...> «.-..... ,,'.; ..“ ._ _. .__- na -, ........, ...... ~ ..m - .. ~> .._........... -..... .... .. ..._ v. 'l '7302511-6 20 l ,, l-; l r šëÉEE2l_2 A. A mouldable sheet was prepared from the following composition, containing a surplus of isocyanate-reactive groups in relation to isocyanate groups, similar to that described in Example 1. 28.5 g styrene vi 2 46.5 g of unsaturated pélyester sts with a hyaroxyl number of Pclynaster 69.5 mg KOH / g and an acid number of 55 mg KOH / g 1188 i.e. 5.78 x 10 -2 moles of isocyanate-reactive (hydroxyl) groups 11.7 g of polyisoeyanate of the same kind as that used in Example 1, i.e. 8.57 x 10 ”2 moles of isocyanate groups 15.5 g of oxypropylated bisphenol A of the same kind as that of Example » pile 1 used, i.e. 7.9 x 10 -2 moles of isocyanate-reactive (hydroxyl) § groups' I I tertiary butyl peroctoate 1 a The stannous octoate and nebutyl alcohol were omitted.

The disc formed was flexible, non-sticky and malleable, could be formed by hand over a mold and could be very easily molded at low pressure. 2 In the composition,% (a - 1) = 0.5 and X = 0.55, ie % (G - 1) was in the range X É 0.15 according to the present invention.

B. The procedure described under AQ) above was repeated, with except that 12.5 g of polyisocyanate (ie 9 x 10 per) and 12.7 g of oxypropylated bisphenol A (i.e. 7.54 x 10 natreactive groups) were used.

A flexible, non-sticky, malleable disc was formed, which was mainly Thing similar to the one obtained according to A.).

In the composition, å (a _ 1) was = 0.24 and X = 0.55, ie 'r (G-- 1) was in the range X 3 0.15 according to the present invention.

C, The procedure described above, under A.) was repeated, with a assumption that 19 g of styrene, 21 g of unsaturated polyester (5.85 x 10 -2 mol is (active (hydroxyl) groups), 19.1 g of the polyisocyanate (1 μmol of isocyanate groups) and 50.9 g of oxypropylated Msphenol A. (1 V '-3 Ü' 1 mol of isooyanate reactive (hydroxyl) groups) was used.

A flexible, non-sticky, malleable disc was formed, which was in the head. similar to that obtained by Experiment A.

In the composition,% (G - 1) = 0.295 and X = 0.55, ie % (m - 1) was in the range X É 0.15 according to the present invention. í-> r PÛOH 'QUALITY -nni f; 'H- “vwn-r - l-l \ 7302511-s Example 4 A. A mouldable sheet was prepared from the following composition, containing an excess of isocyanate-reactive groups in proportion to isocyanate groups, similar to that described in Example 1 above. l 'y 26.2 g of styrene 48.8 g of unsaturated polyester resin with a new hydroxyl number of 85 mg KOH / g and an acid number of 41.5 mg KOH / g i.e. 7.25 x 10 -2 moles of isocyanate reactive (hydroxyl) groups 15 g of polyisocyanate of the same kind as in the example ä Apolit 952 1 use, i.e. 9.45 x 10 -2 moles of isocyanate groups 12 g of oxypropylated bisphenol A of the same kind as denii accordingly using Example 1, 2 i.e. 7.12 x 10 -2 moles of isocyanate-reactive (hydroxyl) groups 1 g of tertiary butyl peroctoate. ~ The standard lactate and the n-butyl alcohol were omitted.

The disc formed was flexible, non-sticky and malleable, could be shaped by hand over a mold and could very easily be ïormpres- sas attached pressure. The board could be cured to a rigid product by heating on similar to that described in Example 1 above.

In the composition,% (a - 1) = 0.26 and X = 0.55, i.e. 1 i (d _ 4) was within nnnddetx i 0.15. according to the present invention. g, B. For the sake of comparison, the above described under A was repeated: procedure, except that 17.7 g of polyisocyanate (ie 1.29 x 10 moles of isocyanate groups) and 7.3 g of oxypropylated bisphenol A (ie 4.55 x 10 -2 moles of isocyanate-reactive (hydroxyl) groups) were used.

The composition contained an excess of isocyanate groups in holding to isocyanate-reactive groups. The disc taken from Ü the shape was non-sticky. However, it was, in contrast to the record I H according to A, very rigid and could be formed by compression molding F only with the use of high pressures. '2 In the composition,% (å - 1) = 0.05 and X, = 0.55, ie % (å - 1) was outside the range X 1 0.15 according to the present invention § ning, 5 Example 2 * A. A mouldable sheet was prepared from a composition containing an excess of the isocyanate-active group relative to isocyanate groups, similar to those described in Example 4A, F ä ~. -. an ... e. s-. v ... - .. nnkeiinna-sh- 1 V 0- D 1 a. groups, similar to those described in Example 5A, except 7302511-6 i 22 *> ~ ~~~~~~~~ f - ~ - ~~ _ \ ______ \ except that 17.5 g of styrene, 52.5 g of unsaturated polyester resin (ie 4.82 x 10-2 moles of isocyanate-reactive (hydroxyl) groups), 20.4 g polyisocyanate (ie 1.48 x 10 9 moles of isocyanate groups) and 29.6 g of oxyacyanate propylated bisphenol A (ie 1.76 x 10 -1 mol isocyanate reactive (hydroxyl) groups) were used. - F The disc that was formed was essentially the same as that in the example 4A.

In the composition,% (Q - 1) = 0.25 and X = 0.55, ie % (Q - 1) was in the range X É 0.15 according to the present invention.

B. For comparison, the process described under A above was repeated. except that 27.6 g of polyisocyanate (ie 2.01 x 10 isoeyana groups) and 22.4 g of oxypropylene bisphenol A (section 1.55 x 10 moles of isocyanate-reactive (hydroxyl) groups) were used. I 1 The disc taken from the mold, and made from one composition, containing an excess of isocyanate groups in ratio f to isocyanate-reactive groups, was non-tacky. However it was, in contrast to the disc according to A, very stiff and could mas by means of molding only with the use of high pressures. _ In the composition, å (å _ 1) - 0.05 and x = 0.55, of i: (yet) was outside the range X in 0.15 of the present invention.

Example 6 A moldable sheet was prepared from a composition containing an excess of isocyanate groups relative to the isocyanate reaction -qT-Tñ ._... p ... 19 g of styrene, 551 g of non-woven polyester (of 5.91 x 10 isocyanate-reactive (hydroxyl) groups), 55 g of polyisocyanate (ie 2.54 x 10 10 moles of isocyanate groups) and 15 g of oxypropylated bisphenol A 3 (ie 8.95 x 10 -2 moles of isocyenate reactive (hydroxyl) groups) were used. å The moldable, iokea-sticky disc that was formed was essentially the same as that described in Example 5A, although a slightly higher pressure was formed by compression molding.

In the composition,% (å - 1) = 0.48 and X - 0.55, ie % (å - 1) was in the range_X É 0.15 according to the present invention. Example 2 In four separate experiments (A - D) discs were prepared from kom » positions similar to that described in Example 5A, by ounces assumption that 24.7 g of styrene, 40.5 g of unsaturated polyester (ie 5.00 x 10'2É) moles of isocyanate-reactive (hydroxyl) groups), 1 g of tertiary butyl peroctoate, 0.5 g of stannous octoate and 0.1 g of hydroquinone were used. Instead of it oxypropylated bisphenol A used according to Example 5 A, they were used -y-.w- IN ,. 7302511 'G Amounts of oxypropylated trimethylolpropane (molecular weight = 510), which listed in the table below, as well as the amounts of polyisocyanate, as shown in this table, were used in the separate experiments.

The composition was mixed and degassed in a similar manner to described in Example 1 and formed into a 5 mm thick layer of * lan polyethylene sheets and allowed to stand at room temperature for 24 hours.s Then the polyethylene sheets were removed to each of experiments A - D leave non-sticky, flexible discs, as light could be formed by hand over a mold or compression molded at low pressure.

The boards could be cured into rigid products by heating on equal as described in Example 1. In each of the experiments A - D the value of X was 0,85 and the value of% C ü - 1) or % (å - 1), which was now the case, within the range X É 0.15, in even similar to what is stipulated in the present invention.

For comparison, it was repeated above, in experiments A - D described procedure, in four additional experiments E - H, with assuming that the amounts of -oxypropylated trimethylolpropane and polyiso- The cyanates used were those shown in the table.

The discs formed in experiments E, F and G were very sty-_ va, could not without difficulty be formed by hand and could be molded only with the use of high pressures. a The disc formed in Experiment H was very sticky, resin adhered to the polyethylene board and when the board was hung had resin a tendency to run off from there.

In each of the experiments E - H was the value for 1 % (a _ 1) or a (å - 1), which was the case now, outside the range X is 0.15, which is required in accordance with the invention. '7302511-6 24 m; lom fl> m uuoxwnw> m > m7um fl mæ0om fl æH0m 36 .. To .. x 3. » »SH .73 Euå Nää m mæ.o I wmm_o fl | c fi X mH ~ H m ~ mH Hlo fl æw ~ H m_mH Q _mw.o I mmo.o Atea N Nw.H N.NN fl loa wN ~ fl æ_N fl W mw ~ o mm.o I fi4 oH N mo ~ N N_mN Nlc fl .æm ~ m m.w W 36 ä ... | 73 x So Nm N13 must ... m n mæ.o I Nm ~ o Nlo fl N mm.m m ~ NH alo fl. _m fl ~ N N.NN U m® ~ o | mNæ ~ o Nlc fl 3 wß.m v ~ mH fl lo fi mo_N m. fl N N 35 | mi ... 13 x .SJV 15 73 So must fl 4 A fl u fi v Nxa ^ H | av-w \ H Hmmm = um | O0ZŶ m nwmm5um | mO m uøwä N. ummm fl um nmmø fl nm HOE Huvud fl oä Husum l fl wwmxm uumnmmuom fi m> fl u% w %% Mmmwv% mø fi m unm>: m cmmonm fl oaæuwë fl nu ba uuoxmHw> n H fi wmäwxm fi Ußnm fl æmonm fi xo 7302511-6 25 __ _ Example 8 In three more experiments, which have the task of further illustrating the invention, the procedure described in the examples was repeated 7A, 7B and 70 above, using oxypropylated glycerol with a molecular weight of 510 instead of the oxypropylated trimethylol nen. Non-sticky, flexible, easily mouldable discs were obtained. For comparison, Examples 7E, 7F, 7G and 7H were repeated with use of oxypropylated glycerol with a molecular weight of 510 in starch for the oxypropylated trimethylolpropane, with substantially similar results as a result.

Exem el A composition of the type described in Example 73 was carefully mixed full of 100 g of powdered calcite (Omya "Millicarb", Plastichem Ltd) and the resulting mixture was degassed and spread on a glass fiber mat in a manner similar to that described in Example 2.

The impregnated carpet was left untouched for 24 hours.

The resulting sheet was non-sticky and could be shaped by hand over a form. The disk was compression molded at a temperature of 120 ° C below 5 minutes at an applied pressure of 14 kp / omg to form a rigid shaped product.

B. For the sake of comparison, the above procedure was repeated according to A except that a composition of the slurry described in Example 7G goat was used.

The resulting disc was non-sticky, but stiff, it could not ~ is shaped by hand over a mold and could only be molded using very high pressures.

C. For further comparative purposes, the above was repeated procedure according to A, except that a composition according to pel 7H was used. Although the resulting disc could easily be shaped, it was sticky and when it was compression molded and heated to cure the resin. set gave it a product with an uneven distribution of the fibers.

Example 10 A moldable sheet was prepared from a composition containing an excess of isocyanate-reactive groups relative to isocyanate nat groups, similar to those described in Example 5, with the exception of of 24.6 g of styrene, 40.4 g of unsaturated polyester resin (5.00 x 10 isocyanate-reactive (hydroxyl) groups), 9.5 g of polyisocyanate, 1 g of tertiary butyl peroctoate, 0.5 g of stannous octoate and 0.1 g of hydroquinone and instead of the oxypropylated bisphenol A used in IN 1 ,. 7so2s11es 26 Example 5, 25.5 g of a polyol having a hydroxyl number of was used 595 mg roa / green an oH functional analyte of 5.5, prepared by oxypropylation of a mixture of toluenediamine and glycerol (ie 1.80 x 10 -4 moles of isocyanate-reactive (hydroxyl) groups).

The resulting disc, which was prepared in a similar manner to described in Example 7, was non-sticky, could be draped by hand over a mold, could be compression molded at low pressures and could be heated. taken in a manner similar to that described in Example 1 to give one rigid product. - In the composition, x = 1.10 and a (f: -_1) = 1.17, par å (ü - 1) was in the range X É 0.15 according to the present invention.

Example 11 f A. A mouldable sheet was prepared from a composition containing an excess of isocyanate-reactive groups relative to isocyanate groups, similar to that described in Example 5, with except that 24.6 g of styrene, 40.4 g of unsaturated polyester (ie 5.00 x 10'2 moles of isocyanate-reactive (hydroxyl) groups), 15.52 g of polyisoyanate (ie 9.85 x 10 -2 moles of isocyanate groups), 18.1 g of oxypropylated bisphenol A (ie 1.08.x 10 -1 mol of isocyanate-reactive (hydroxyl) groups), 1 g tertiary butyl peroctoate, 0.5 g of stannous octoate and 0.1 g of hydroquinone an- was reversed, and in addition the composition contained 3.58 g of phenyl isocyanate (ie 2.84 x 10 -2 moles of isocyanate groups). 5 The resulting disc, which was prepared in a similar manner to described in Example 7, was non-tacky and readily malleable and was in substantially similar to the disc obtained in accordance with Example 10.

In the composition, X = 0.55 and the value of % (a-1) + ßy + §y = o, 2a5, i.e. in the range X 3 0.15 in accordance with the present invention.

B. For the sake of comparison, the one described above under A was repeated procedure, except that 16.1 g of polyisocyanate (i.e. 1ê175 x 10O'1 moles of isocyanate groups), 4.0 g of phenyl isocyanate (ie 5.36 x 10 cyanate groups and, instead of the oxypropylated bisphenol A, 14.9 g of oxypropylated trimethylolpropane having a molecular weight of 510 (ie 1.44 x 10 "1 mol of isoeyanate reactive (hydroxyl) groups) was used.

The resulting disc, which was prepared in a similar manner to described in Example 7, was non-sticky, but very stiff, could not draped by hand over a mold and could be molded by compression molding (only using very high pressures. 7302511 -6 27 ._ ..

F In the composition, X = 0.85 and the value for % (° ß-1) + ßv + -Ü¿v = 0.511 +, of outside the range x f. 0.15 in accordance with the present invention.

Claims (2)

730251146 28 Patentk-rav A molding composition for the manufacture of plastic articles, formed from a mixture containing; (a) 5-95% by weight of precursors to a polyurethane containing at least one polyfunctional compound containing groups which are reactive with respect to isocyanate groups, and at least one polyisocyanate, the functionalities of the polyfunctional compounds and of the polyisoeyanates amounting to 2-5 and the functionality of at least one of the polyfunctional compounds and / or at least one of the polyisocyanates is greater than 2, and in (b) 95-5% by weight precursors of a cured polyester resin, containing at least one ethylenically unsaturated polyester and at least one ethylenic unsaturated monomer, copolymerizable with the ethylenically unsaturated groups of the polyester, a wherein the polyfunctional compound and the polyisocyanate are reacted together with the ethylenically unsaturated polyester, in such cases where the polyester contains isocyanate-reactive groups, to such an extent that a manageable, malleable composition is formed, characterized by the proportions of polyphene functional compound, polyisocyanate and ethylenically unsaturated polyester in the mixture are such that either (1) the number of moles of isocyanate-reactive groups in the polymeric compound plus ethylenically unsaturated polyester, in cases where the polyester contains isocyanate-reactive groups, is greater than the number of moles of isocyanate groups in the polyisocyanate, ooh the ratio Y, i.e. å '(<1 - 1), is in the range X - 0.15 to X + 0.15, where the number of hollow isocyanate-reactive groups in the polyfunctional α compound plus ethylenically unsaturated polyester number of moles of isocyanate groups or (2) the number of moles isocyanate groups in the polyisocyanate are greater than the number of moles of isocyanate-reactive groups in the polyfunctional compound plus ethylenically unsaturated polyester, in cases where the polyester contains isocyanate-reactive groups, and the ratio Z, i.e. i (å- "1), is in the range X - 0.15 to X + 0.15, where the average functionality of the average functionality of the poly-polyisocyanates - 2 functional compounds, reactive x _ _, with isocyanate, - 2 2 i 2. 1 ii vzi6§isi1 1 -s 29 _ rr 2. A forming composition according to claim 1, characterized in that the functionalities of the polyfunctional compounds and polyisocyanates are in the range 2-4. 5. A molding composition according to claim 1 or 2, characterized in that the polyurethane precursors are substantially free of ethereal unsaturation. 4. A molding composition according to any one of claims 4-5, characterized in that the ethylenically unsaturated polyester in each molecule contains at least two groups which are reactive with respect to ioocyanate. '' Molding composition according to one or more of Claims 1 to 4, characterized in that the polyfunctional compound and the polyisocyanate are substantially completely reacted together with the ethylenically unsaturated polyester, in those cases where the polyester contains ioocyanate-reactive groups. wherein the ethylenically unsaturated monomer and the ethylenically unsaturated polyeater are substantially unpolymerized. - Forming composition according to one or more of the provisions 1-5, characterized in that it is in the form of a disc. Molding composition according to one or more of Claims 1 to 6, characterized in that the ratio Y or Z is in the range X - 0.1 to X + 0.1. Molding composition according to one or more of Claims 1 to 7, characterized in that it is prepared from a mixture containing 10-50% by weight of polyurethane precursors and 90-50% by weight of cured polyester resin precursors. 9. A forming composition according to any one of claims 1-8, characterized in that the polyfunctional compound is selected from bisphenol A, oxypropylated trimethylolpropene and oxypropylated glycerol. 40. Forming composition according to one or more of the claims 4-9, k 'a'. n n e t e c k n a d that the polyisocyanate contains an isocyanate with the structure OGN NCO Ü B <3 / where B represents a divalent group. 1? Zo2s11-s 30 Molding composition according to one or more of Claims 1 to 10, 'characterized in that the mixture of polyurethane precursors and cured polyester resin precursors contains at least one monofunctional isocyanate and / or a monofunctional, isocyanate-reactive compound and that either' ( 1) the number of moles of isocyanate-reactive groups in the polyfunctional compound plus monofunctional isocyanate-reactive compound, if present, plus ethylenically unsaturated polyester, in cases where the polyester contains isocyanate-reactive groups, greater than the number of moles of isocyanate groups in the polyisocyanate plus monofunctional isocyanate such is present, and the ratio Ti, i.e. ' fl- (o fl -1) + on'ß + å-, 'y' is in the range X - 0.15 to X + 0.15, of, ß and v have the meanings given below, namely the number of moles of ieooyanate-reactive groups in the the polyfunctional compound plus the ethylenically unsaturated polyester plus the monofunctional, isocyanate-reactive compound number of moles of isocyanate groups in the polyisocyanate plus the monofunctional isooyanate number of moles of monofunctional isocyanate-reactive compound moles of monofunctional derivative number of moles of isooyanate groups in the polyisocyanate plus the monofunctional isooyanate or (2) the number of moles of isooyanate groups in the polyisocyanate plus monofunctional isocyanate, if present, is greater than the number of moles of isocyanate active papers in the polyfunctional compound , if such is present, plus ethnic omä polyester, in such cases where the polyester contains isocyanate-reactive groups, and the ratio Z ', i.e. å- (åå -1) + or.'ß + å-1 ¥ _ lies within the range X - 0.15 to X + 0.15, where on ', ß and y have the meanings given above. Forming composition according to Claim 11, characterized in that the ratio I 'or Z' is in the range X - 0.1 to X + 0.1. _ | , 31 ê vzozsna-aae Forming composition according to one or more. of claims 4-12, characterized in that it contains a free radical generator. PROMISED PUBLICATIONS: 'Sweden patent applications 16 056/72, 17 058/72 France 1 498 779 i' a v- n »