NO753810L - - Google Patents

Description

It is known from the past to produce phenol pressing compound or

malleable mixtures of phenol, and two different types of phenol formaldehyde condensate have been used for many years, namely novolaks and resols. The novolaks have been produced by condensing formaldehyde and phenol in a molar ratio of approx. 1 to 1 or something

lower conditions, and usually in the presence of an acidic condensing agent. The condensation is carried out almost completely, so that the novolak becomes water-insoluble and can be separated from the associated water and used for the composition of a malleable mixture by mixing with a curing agent, usually hexamethylene -tetraamine and other additives such as fillers, reinforcements and release agents. Molded pieces are then produced in suitable forms using the so-called "hot press" process which was developed in its time by Kaekeland.

Molds have also been prepared from resoles by a casting technique using partial condensations of formaldehyde and phenol in high mole ratios, allowing at least about 1355. Condensation is carried out by waiting, usually in the presence of

a fixed alkaline condensing agent. Condensation is interrupted by wished. end point by interrupting the heating and by acidifying to one. Desired pH value, where the condensation at room temperature is

relatively '■slow' The casting can then be produced from

the partial condensate by adding "hardeners", for example a solution of hydrochloric or phosphoric acid in glycerol or in a glycol, after which the resulting mixture is poured into a mold. Curing takes place at ambient temperature or a slightly higher temperature." A detailed discussion of phenol orrnaldehyde condensates is found in Ibe Chemistry of Phenolic Resins, Martin, John tJiley & Sons, Inc, 1956 and the references therein mentioned.,

. It has previously, see US patent 3,502,610, also proposed that laminate, coating', molded pieces and expanded foam can be produced from

a polyhydric phenolaldehyde resin containing 2-6% hydraulic

cement, based on the weight of the polyhydric phenol. The cement is said to lower the resin's viscosity and give it high-temperature strength and fireproof properties."

The present invention has provided resins containing stoichiometric amounts of cement. This applies both in that case, . where the Sikrpixen is produced before the addition of cement or where the cement is mixed with monomers before the resin is produced. The fact that according to the invention stoichiometric quantities of cement are used means that sufficient cement is available to be able to react with all the water that is initially present in the system plus any reaction water that is formed during hardening of the system.

In one system, the resin is produced for. mixing of cement. In what follows, these systems will be referred to as "resin systems". ■ In another embodiment, the cement is mixed with monomers. before the resin is produced.. These systems will be named in the following

"monomeric system". Both systems have excellent fireproof properties and produce small amounts of smoke. They have physical properties - which can be compared to conventional phenolic pressing compounds.

In one further embodiment, the strength properties of these systems have been improved by the fact that in the malleable mixtures, introduced bridging agents of at least one of the following two components, namely (a) an organosilane containing at least two hydrolyzable silane groups where the distance between any two hydrolysis sites on a glass fiber is greater than the distance between any two hydrolyzable silane group in the organosilane, and. (b) an aminoalkylsilane.

In a further embodiment, the form tension properties are further improved and the surface contamination in these systems is reduced by producing a mixture containing resin, cement and clay.

The resin can be a phenolformaldehyde condensate, phenolaminoplast formaldehyde condensate, aminoplast formaldehyde condensate, furfural condensate, furfuryl alcohol condensate or resorcinol formaldehyde condensate or a phenol aminoplast formaldehyde condensate.

The molar ratio between formaldehyde and phenol can be varied within wide limits when producing the resins according to the invention.

In reality, in a context, there is no other limit for this purpose depending on the fact that Portland cement has been found and hardens formaldehyde to a non-fusible state. In practical terms, it is preferred that the molar ratio of formaldehyde to phenol lies in the interval from 1:1 to 5:1. Most desirable is that this ratio lies in the interval from 1.5:1 to 3:1.

The resins according to the invention are well suited for use as steelier mixtures and especially when used for use in

a closed form. Hardening or stiffening of the cement takes place with wood

hydration. For hardening of the large amount of cement in the resins according to the invention, the presence of large amounts of water is required. During the shaping or casting, the cement comes from the malleable mixture and removes any water obtained during the condensation or hardening. This does not apply to resins according to U.S. Patent 3,052,610 which contain only small amounts of hydraulic cement, flown resins can be used only in open forms where water can be removed to the atmosphere.

These malleable mixtures have good fireproof properties and low smoke development and they can be used for the production of panels, utility items such as f.e. bathtubs and for coverings.

Clay is a naturally occurring sediment or a sedimentary rock consisting of one or more minerals and additional compounds

as the clay usually contains hydrous aluminum oxide or iron oxide in copious amounts, preferably in particles of colloidal or nearly colloidal size and which usually exhibits plasticity, when the clay is sufficiently pulverized and moistened. Later studies have led to clay minerals being divided into four crystalline groups and an ikf^e-crystalline group, namely (1)

the kaolin group, (2) the montmorillonite group, (3) the illite, btfavasite or hydromica group (the terms are used interchangeably),

(4) the attapulgite group and (5) the allgfan group, which constitutes the non-crystalline group. The clays used in the present invention belong to the crystalline kaolin group. More

more precisely, the kaolins used are classified as ceramic clays. Ceramic clays mean clays that include reminent kaolin clays, sedimentary kaolin clays, ball clays, fire clays and clays for porcel. a semal you. It has been found that a clay with the designation Old. My grins. 4 Ball Clay from Kentucky-Tennessee Clay Cq.? Mayfield, Kentucky, USA is highly suitable for use in the invention. Said clay in its raw state has a medium gray color and in its burnt state a faint gray-white color, cone 12. Typical chemical analysis data for the Old Mine No. 4 Ball Glay clay are:

99% of the particles included in Old Mine No. 4 Ball Clay are finer than 20/u, and 68% of the particles are finer than 1 >u.

The amount of ceramic clay that can be used in a moldable mixture according to the invention lies in the interval from about 5 to about 40 percent by weight of the total weight of the moldable mixture, including the clay. Ceramic clay is preferably present in an amount ranging from about 10 to about 20 percent by weight of the total weight of the moldable mixture <>

Hydraulic cement is generally defined as powdered mixtures

of silicon dioxide, aluminum oxide, quicklime, iron oxide and magnesium oxide,... which hardens when mixed with water. Hydraulic cement includes Portland cement, calcium aluminate, magnesium oxide, natural masonry cement, porcelain and slag cement. In the present context, the term "cement" means all types of hydraulic cement and cement products © Cement products used in the present context include the building materials. The active or hardening ingredients are magnesium or calcium derivatives. Commonly used cement products include burnt lime products and gypsum products. As previously mentioned, the invention can be practiced with which of the two systems.

The two systems are, as mentioned, the monomeric system, and the former

said resin system. In both cases, the amount of cement added is in the interval from about 1 to about 20 parts by weight of cement per part by weight of total water in each system.

In the monomeric systorrx, the resin is formed in contact with the cement. Depending on the percentage of water in the aldehyde-water solution used, it may be necessary either to add additional water or to remove a certain amount of the reaction water. The total amount of water

in this system is adjusted to fall in the range of about 0.15 to about 5 moles of total water content per pol aldehyde in the system.

In the resin system, the resin is prepared before it is mixed with cement.

In this system, the total flow rate is determined, after which water adjustment is carried out and cement is added in accordance with this.

Supply or removal of water may or may not be necessary. The total amount of water in this system is determined as follows: A sample of the resin is placed in an aluminum weighing pan and the initial weight is determined. Place the aluminum weighing pan and its contents

. then in an oven and dried at about 110°C for a time of about

3 hours 6 The aluminum weighing pan is removed from the oven, brought to room temperature and a final weight determination is made. The remaining resin consists of a hardened, solid mass. Then to be determined

the percentage of. solids in the resin by dividing the final weight by the initial weight. If one assumes that stoichiometric ratios

exists between all components and that mainly 100%

reaction is effected, it can be assumed that water constitutes the total percentage of volatile constituents (100% solids)'. The percentage amount of volatile substances multiplied by the initial weight of the resin therefore gives the total amount of water in the resin system.

The moldable mixtures according to the invention may contain 0.01 to 10.0 percent by weight of bridging components based on the total weight of the moldable mixtures. This amount is* preferably from 0.01 to 5% by weight.

KMa concerning the bridging agents is a particularly suitable aminoalkyd silane

gamm.α-aminopropyltriethoxysilane which is commercially available from Union Carbide under the product designation "A-1100" and from General Electric under the product designation "SC-3900". A commercially available N-beta(aminoethyl) gamma-aminopropyl trimethoxy oxalate

from Union Carbide under the product designation "A-1120" and from Dow

•Corning under the designation "Z-6020" is also suitable.

'..The organosilane containing at least two hydrolyzable silane groups with the formula •

where each R represents an alkyl or aryl group containing from 1 to 10 carbon atoms and R' is an alkylene or phenylene group containing from 1 to 15 carbon atoms are also suitable. A particularly suitable other silane bridging agent is bis(B-trimethax-.silylethyl)benzene having the formula (

The workable mixtures according to the invention can be shaped or molded using any suitable molding process. ■ They are

particularly suitable for use as mixtures for the formation of .

sheets (SM(S. = sheet molding compound) or mixtures for bulk molding (BMC - bulk roolding compound). When used in this way, the molding compound occurs in an amount from about 10 to about 95 percent by weight of the total weight of the mixture, reinforcement - glass fibers in an amount of' up to about 80, weight percent of the ' total weight of the mixture and fillers in an amount that makes up the rest of the total mixture."

Preferred fillers are calcium carbonate and aluminum oxide.

At both SMC. and BMC. it is advantageous that a mold release agent is added in an amount of up to about 5 percent by weight of the mixture used for sheet forming or building. A particularly suitable mold release agent is zinc stearates.

The following examples further illustrate the invention.

EXAMPLE 1

Phenol and formaldehyde are heated in a reactor, mixed and heated to a temperature of 43.3°C. The calcium oxide catalyst is then added over the course of 2 hours while the temperature is maintained at 43.3°C. The temperature of the reactants was raised to 51.7°C over a 30 minute period and then held at this temperature for a further 90 minutes.The temperature was then raised to 60.0°C over 30 minutes and was held at this temperature until the content of free formaldehyde was in the interval from 7.0 to 7.2 percent by weight. The dicyandiamide was added over a 30 minute period at a temperature of 60.0°C and the reaction mixture was cooled to 40.5°C over the following half hour. The urea was added at 40 6 C and the neutralization was achieved when the temperature was lowered to below 37.8 oC by adding a mixture of 20 weight percent phosphoric acid and 80 weight percent sulfuric acid to a pH value of from 7.2 to 7, 3.

The physical properties of the resin according to example I are the following:

Sl ignore ding 77 seconds

. Free phenol 1.2%.

c

EXAMPLE II

The following materials were mixed in a stainless steel container. steel:

The resulting mixture was dispensed simultaneously with a chopped glass fiber strand onto a moving polyester film approximately 61 cm wide and of undetermined length. Another polyester film, also having a width of about 61 µm and of undetermined length, was brought into contact with the upper side of the sheet-like mass of cast glass fiber and resin-cement mixture and was transported along with the mass and the first sheet. Sheets of the mass, ,with a size of about 60.9 x. 50.8 cm and. with a thickness of approximately 3.2 mm was cut from the mass with the polyester films back on each of the two main sides.

Moldings were produced from these sheets between flat matrices adapted to each other, pressing being carried out at 149°C and a pressure of

2

140 kg/cm .....

Sheets produced in accordance with the above were examined for flexural modulus, flexural strength, tensile strength and impact strength.(lEOd test): (1) after forming and (2) after autoclave treatment for 16 hours. The results of these tests appear in the following table"

In the examples, flexural strength and flexural modulus were determined according to ASTM Specification D790, tensile strength according to ASTM Specification D638. and impact resistance according to ASTM Specification D256. guess result shows that the thermosetting resins according to the present invention have physical properties that make them very well suited for use as moldable mixtures. The shaped articles were found to be fireproof and exhibit low smoke generation and they could be easily cured in a closed mold.

EXAMPLE III

A phenol urea formaldehyde condensate was prepared from 1240 parts phenol, 2600 parts 52% formaldehyde, - 2500 parts Portland cement,

1290 parts carbamide, 2500 parts gypsum cement,. 2500 parts aluminum oxide, 400 zinc stearate and 800 parts ice. The phenol, formaldehyde, carbamide and 100 dffifcers of Portland cement were introduced into a stainless steel vessel fitted with a propeller type stirrer and an indirect heat exchanger. This batch of mixture was stirred for 18 hours during which cooling water was circulated through the indirect heat exchanger to maintain the temperature of the mixture at approximately 68°C.

After the preliminary 18 hour reaction period, the reaction products in the container were added to the rest of the Portland cement, the gypsum, the aluminum oxide, the zinc stearate and the ice. The obtained mixture, which was a phenol formaldehyde condensate, together with chopped glass fiber strand, was deposited on a moving polyester film with a width of approx.

60.9 cm and undetermined length. The fibers were made of glass sintered containing 54% SiO2, 14% Al^, 4.5% MgO, 17.5% CaO and 10% They were coated with polyester finishing agent containing a

t lubricant and gamma-aminopropylitiriethoxy^aP-sn. Another polyester film, also with a width of approximately 60.9 cm and unspecified length,'

was brought into contact with the upper side of the sheet-like mass of-'-deposited ifjiass fibers and phenol formaldehyde condensate and was transported-

together with the mass and the first sheet» Sheet a,v the condensate mass and the glass fibers ("Sheet Molding Compound") were cut from the mass in a size of approximately 60.9 x 50.8 cm and with a thickness of approximately 352 mm (1/ 8"), the polyester films remaining on the two main sides. Molded bodies were produced from these sheets between mutually adapted planar matrices at a temperature of 149°C during 5 minutes and a pressure of 19.9 kg/cm 2 ;.

Sheets prepared according to the above were tested for flexural modulus (ASTM -D-790), bending strength, tensile strength, (ASTM D-638) and impact strength (Iaod test, ASTM D-256). For this, an examination was partly carried out (1) after forming and partly (2) after the sheets had been autoclaved for 16 hours at a temperature of 108°C

■and (3) after they had been immersed in boiling water for 2 hours. The results of these tests are summarized in the following table for different ratios between glass fibers and phenol formaldehyde condensate.

It has been found that the phenol condensate obtained in the manner described above has a sufficiently long shelf life that, under the current ambient conditions, the press pulp sheet produced therefrom should last satisfactorily for a period of 4 hours, and that the malleable the mixture itself has a shelf life of More than

3 weeks... It is realized that this is a sufficiently long time to completely satisfactorily "use the material for the production of sheets, plates or other shaped pieces"

Qpplysnirtgoneni the preceding table shows an unexpected result:

a relatively small reduction in the strength of the front parts - accordingly.

to the indicated numbers. after 2 hours of autoclaving at 10S oC and

2. hours in boiling water indicates that the "jlass fibers are not significant affected by the cement" This is unexpected due to the fact that glass fibers with the specified saranth content, distributed sos reinforcement in an aqueous mixture consisting of equal parts of Portland and gypsum^seméft in it,

least to some extent should be destroyed by 108°C autoclaving i

16 hours» The figures in the previous table show, on the other hand, that during autoclaving or boiling no more than a small

, cHslaying of the fibers.

Por to show the excellent fire safety of molded pieces produced

according to. the process in example ill, panels were produced and examined with regard to flame spread's heat contribution and smoke development 1. comparison with panels of other commercially manufactured products. The panels according to the invention are - produced from a phenolcarbamide formaldehyde condensate - produced according to example ilX sed as a starting point from the mixture indicated therein met;

an addition of 20 parts of 1,2-bis-trimethoxysilylethane. Plates or sheets were produced according to example IV from the obtained condensate and glass fibers (the glass fibers were produced from a glass of the composition indicated in Example 1 and coated with a polyester coating agent containing ganrøawaetaJcryloxypropyl trime took sy-silane) was deposited sanraen with the condensate in such quantity ratios that the gl a-g sf fibers made up mainly 22% sv .fcondonsatefc cg the fibers. Panels with a size of 60jS x 50.8 cm and a thickness of 3*2 Stm were then formed from the obtained sheets under the following condition:

143°C for 5 minutes at a pressure of 60 tons. These panels were fixed in a tunnel test according to ASTM E-84 in relation to panels of the currently marketed type, whereby the following results were obtained:

In each case, a low number for the tunnel test E-84 is a better value than a flat number.

EXAMPLE IV

This example illustrates the monomeric system in which a combination of cement was used. The following ingredients are used.

The ingredients can be mixed in any order and with

an arbitrary mixing process. However, it is preferred to ©.add 1

the cement in two stages to enable the exothermic reaction to be controlled, thereby avoiding immediate hardening of the cement.

In this example, 94 g of phenol, 144.2 g of 52% solution were added

of formaldehyde in water, 45 g water and 10 g Portiand cement to a beaker at room temperature. BJLandingen was stirred up and. the exothermic reaction began immediately"

The beaker was water-cooled to prevent heating to a temperature above 60°C. The mixture was then cooled to room temperature and at this time the remaining 161.3 g of Portland cement and 171.3 g of gypsum cement were added to the beaker under stirring. The. the product obtained was in the form of a moldable mixture. The gypsum cement used was "Hydracal B-II" sold by United States Gypsum.

EXAMPLE V

8.7 g of gamma-aminopropyltriethoxysilane was added to 580-.8 g of the monomeric system-according to Example I. The addition was made

at room temperature in a beaker with stirring. The product formed was obtained in the form of a malleable mixture. The gamma-amine Eprepyl triethoxysilane used was "A-1100" from Union Carbide.

EXAMPLE VI

8.7 g of bis(B-trimethoxysilylethyl)benzene, a silane bridging agent with two hydrolyzable silane groups, was added to 580.8 g of the monomer system according to example I. The addition was made at room temperature in a beaker with stirring. The product formed was obtained in the form of a malleable mixture.. -

EXAMPLE VII •

4.35 g of gamma-aminopropyltriethoxysilane and 435 g of bis(B-trimethoxy-silylethyl)benzene, a silane bridging agent with two hydrolyzable silane groups, were added to 580.8 g of the monomer system according to

example I. The addition was made with stirring in a beaker at room temperature. The product formed was obtained in the form of a malleable mixture. The gamma-arainopropyltriethoxysilane used was "A-1100" from Union Carbide*

EXAMPLE VIII

.500 g of the resin of Example I, 2500 g of Portland cement and 2500 g of gypsum cement were poured into a stainless steel container at room temperature with stirring. The product formed was in the form of a malleable mixture.

J

EXAMPLE IX

5.25 g of gamma-aminopropyltriethoxysilane was added to 350 g of the resin system according to Example VI. The supply was made at room temperature in a beaker with stirring. The product formed was obtained in the form of a moldable mixture. As gamma-aminopropyl triethoxysilane, "A-1100" from Union Carbide was used.

EXAMPLE X

5.25 g of bis(B-trimethoxy<y>sil<y>iLetyl )benaene, a silane bridging agent with. two hydrolyzable silane groups, was added to 350 g of the resin system in example VI. The supply was made at room temperature in a beaker with stirring and the product obtained was in the form of a moldable mixture.

EXAMPLE XI

2.62 g of gamma-aminopropyltriethoxysilane and 2.62 g of bis(B-trimethoxysilylethyl)benzene were added to 350 g of the resin system of Example VI. The supply was made at room temperature in a beaker while stirring. The product formed was obtained in the form of a moldable mixture.

EXAMPLE XII

This example illustrates the incorporation of a resin system into a pressed sheet compound (SMC). The following ingredients were used:

The ingredients may be mixed in any order and by any suitable mixing process. In this example, however, the mixing was carried out in the following way.- The resin was first poured at room temperature into a stainless steel mixing container. The gamma-aminopropyltriethoxysilane and bis(B-trimethoxysilylethyl)benzene were then added with stirring. While stirring continued and room temperature was maintained, the alumina and then the zinc stearate were added. The resulting mixture, together with chopped glass fiber strand, was deposited on a moving polyethylene film with a width of approximately 61 cm and an undetermined length. Another polyethylene film also with a width of 61 cm and of undetermined length was brought into contact with the upper side of the sheet-like or plate-like mass of deposited glass fibers and resin-cement mixture. said surface and transported together with the mass and the first film. Sheets of the pulp, measuring approximately 61 x 51 cm and a thickness of approximately 3.2 mm, were cut from the pulp and with the polyethylene film back on the two flat sides* Shaped products were made from these sheets between planes matched matrices as the forming was carried out during 5 minutes at 149°C and under a pressure of 70 kg/cm^. Sheets produced according to the above Me examined with regard to flexural modulus, flexural strength, tensile strength and slSfgf strength (Iaod test) both (1) after forming, and (2) after the sheets had been treated in an autoclave for 16 hours at a ' temperature of 108°C. The results of these tests are summarized in the following table and are compared with a file trap where the sheets or discs were produced from a moldable mixture containing the same resin system but without bridging agents.

In the examples, the flexural strength and flexural modulus were determined according to ASTM Specification D 790, the tensile strength according to ASTM Specification D 638 and the impact strength according to ASTM Specification D 256.

These results show that the stoppable mixtures according to the invention have physical properties which make them very well suited as malleable mixtures. The molded articles were found to be fire resistant, give little smoke development and have improved strength. Moreover, the shaped objects could easily be cured in a "closed mold.

EXAMPLE XIII

• This example shows the best method for producing a malleable mixture according to the invention and its use as a press sheet mixture (SMC). The following ingredients were used:

The above ingredients can be mixed in any order

and with any suitable mixing process.- In this case, however, the mixing was carried out in the following manner: The hoppix was.-first hot in a stainless steel mixing container at room temperature. Then, the total amount of Portland cement and the total amount of gypsum cement were sequentially added to the container at room temperature and with stirring. While stirring continued and room temperature was maintained, the ceramic clay and zinc stearate were added followed by the two bridging agents. The product obtained was a moldable mixture. The ceramic clay used was "Old Mine no.

4 Ball Clay". As gypsum cement, "Hydracal B-ll" from

United States Gypsura-Corp. As gamma-aminopropyltriethoxysilane

Me used "A-110Q?' and as tetraethoxysilane, tetraethyl orthosilicate P was used, both from Union Carbide Corporation"

.The ingredients were dispensed onto a moving polyethylene film approximately 61 cm wide and of undetermined length. Another polyethylene film, also with a width of 61 cm. and undetermined length, was brought into contact ... with the upper side of the sheet-like or plate-like mass of deposited glass fibers and resin-cement mixture and was transported together with the pulp and the first film. Sheets or slabs of the pulp with a size of 61 x 51 cm and a thickness of approximately 3.2 mm was cut from the mass with the polyethylene films back on both flat sides of the mass. Molded pieces were produced from these sheets or plates between flat, mutually fitted matrix pieces, while the forming was carried out within 3 minutes at. a temperature of 149°C and a pressure of 65.0 kg/cm<2.>Very little was noted surface of contamination for the obtained molded body.

EXAMPLE XVI

This example shows a method for producing a moldable mixture according to the invention. The following ingredients were used:

The above-mentioned ingredients were mixed using the same method as in Example XIII. The glass fibers were added with continuous stirring at room temperature after adding the silane bridging agent. Stirring was continued until the glass fibers were completely dispersed. The mixture obtained consisted of a bulk forming mixture (BMC). The individual glass fibers used had a length ranging from about 3.2 mm to about 3.18 cm and a diameter of from about 63.5 x 10 g-cm to about

—6 ■ '

759 x 10 cm. As ceramic clay, 1.Qld Mine No. 4 Ball Clay was used. As gypsum cement, "Hydracal B-ll" was used. As gamma-aminopropyl triethoxysilane, "A-1100" was used, and as tetraethoxysilane, tetraethyl orthosilicate was used.;

A quantity of the obtained mixture of about 1000 g was placed

in a heated form. A planar mold of size approximately 31 x 46 cm and a thickness of 3.2 mm was produced between two piaae

matrices adapted to each other. The formation was. carried out within 3 minutes at a temperature of 3.49°C and a pressure of 65.0 kg/cm2.

In the mold piece obtained, good mold flow and very little over f iha tea vsmit ting was observed.

EXAMPLE XV

The following example shows the use of the monomer system for the production of a moldable mixture according to the invention. IN

this example, the thermosetting of the resin in contact with the cement was carried out to form a moldable resin cement mixture"

The resulting moldable resin cement mixture was then further modified to form a pressed sheet compound (SMC). Following

ingredients were used:

The ingredients can be mixed in any order and at any time

using any suitable mixing device... However, it is preferred to add the cement in two stages so that the exothermic reaction can be controlled and thus immediate hardening of the cement can be avoided.

In this example, the total amount of phenol and 52% formaldehyde solution as well as deionized water is first poured into a stainless steel mixing vessel at room temperature. * Approximately 10% of: the total amount of Portland cement is then added. The mixture is stirred and the exothermic reaction begins immediately.

The mixing container is then cooled to prevent heating to a temperature above 60°C. The mixture is allowed to cool to room temperature

bg.at this time, the rest of the Portland cement is added to the container while stirring, where the total amount of gypsum cement, - the total amount of gamma-aminopropyltriethoxysilane and the total amount of tetraethoxysilane.

The product obtained is a moldable resin-cement mixture.

While the stirring is taking place, the aforementioned malleable resin-cement mixture is modified by supplying the total amounts of ceramic

clay and zinc stearate. The ceramic clay used is "01de Mine no. 4 Ball Clay".

The ingredients are deposited on a movable polyethylene film with a. width of approximately 61 cm and undetermined length. Another polyethylene film also having a width of approximately 61 cm and undetermined length is brought into contact with the upper side of the sheet-like mass of deposited glass fiber and pitch cement mixture and transported together with the mass and the first sheet.

The product obtained is obtained in the form of a pressed sheet mixture (SMC).

EXAMPLE XVI (Comparison)

In this example, the same ingredients are used as in example XIII with the exception that aluminum oxide is used as a filler instead of ceramic clay. The mixing process was the same as in Example II and the resulting malleable mixture was used as SMC in the same way as in Example XIII. In the molded pieces obtained, a marked surface contamination was observed compared to the molded pieces in example XIII, where only very little surface contamination could be observed..-.

EXAMPLE XVII (Comparison*

In this example, the same ingredients were used as in example XIV with the exception that. aluminum oxide was used as a filler

instead, for ceramic clay. The mixing process was the same as. in example XIV and the obtained bulk-source mixture was shaped on the same set sbm in example XIV.. In the obtained mold piece, poorer mold flow and marked surface contamination were observed in comparison with the mold pieces according to example XIV"where good mold flow and very little surface contamination was observed.

Claims (29)

1. Malleable mixture, characterized by a mixture of (A) a mixture of (1) a thermosetting plastic of at least one of the following condensates, namely phenolformaldehyde condensate, phenolamino piast-formaldehyde condensate, aminoplast formaldehyde condensate. resorcinol formaldehyde condensate and resorcinol-formaldehyde urea condensate, and (2) at least one cement, where the cement is present in quantity i .the range from about 1 to about 20 parts by weight calculated per part by weight of the water content of the curing plastic, or (B) a condensate resin obtained from at least one cement, formaldehyde and at least one of the substances phenol, aminoplasts and resorcinol, where the weight of the cement is from 1 to 20 parts by weight of cement per parts by weight of the water used for the production of the resin, and 3/5 of the weight of the formaldehyde used for the production of the resin. 2. Formable mixture as specified in claim 1, characterized in that the amount of cement is from 1 to 9 parts by weight calculated per part by weight water. 3. Formable■mixture as specified in claim 1, c a r a c t e r i s r e t in that the amount of cement constitutes from 1.5 to 5 parts by weight calculated per part by weight water. 4. Formable mixture as specified in claim 1, characterized by the fact that the weight ratio between thermosetting plastic and cement is in the range from lsl to 1:4. Formable mixture as stated in claim 1, characterized in that the ratio between thermosetting plastic and cement is in the range from 1:1 to 1:3. 6. Formable mixture as stated in claim 1, characterized in that the ratio between thermosetting plastic and cement is 1:2. 3. Moldable mixture as stated in claim 1, characterized in that the thermosetting plastic is made up of phenol formaldehyde condensate or a phenolamino plastic formaldehyde condensate with a molar ratio of formaldehyde to phenol of at least 1:1. 8. Formable mixture as stated in claim 7, characterized in that the molar ratio of formaldehyde to phenol is in the range from 1:1 to 5:1. 9. Moldable mixture as stated in claim 7, characterized in that the molar ratio between formaldehyde and phenol is in the range from 1.5 to 1 to 3 to 1" 10. Formable mixture as stated in claim 1, characterized in that the cement consists of a hydraulic cement or a cement product. 11. Formable mixture as stated in claim 10, characterized in that the hydraulic cement is Portland cement, calcium aluminate cement, magnesium oxide cement or slag cement. 12. Formable mixture as stated in claim 10, characterized in that the cement product is a gypsum. 13. Formable mixture as stated in claim 1, characterized in that the cement comprises a mixture of hydraulic cement and gypsum cement. 14. Moldable mixture as stated in claim 10, characterized in that the hydraulic cement - consists of Portland cement. 15. Moldable mixture as stated in claim 1, characterized in that it comprises from 0.01 to 10.0 percent by weight of a bridging agent calculated on the total weight of the moldable mixture, the bridging agent being provided by at least one of -the following agents namely (a), organosilanes containing at least two hydrolyzable silane groups of which the distance between any two hydrolysis sites on a glass fiber is greater than the distance between any two hydrolyzable silane groups in the organosilanes, and (b) aminoalkylsilanes. 16. Formable mixture as specified in claim 15, characterized by the bridging. aminoalkyl-silane agent is made up of gamma-aminopropyltriethoxysilane. 17. Formable mixture as stated in claim 15, characterized in that the bridging organo-silane agent has the general formula where R represents alkyl or aryl containing from 1 to 10 carbon atoms and R.Ver an alkylated or phenylene group containing from 1 to 15 carbon atoms. .18. Moldable mixture as stated in claim 15, characterized in that the brew-forming agent constitutes .0.01 to 5.0 percent by weight. 19. Moldable mixture as stated in claim 15, characterized in that the bridging row part constitutes 0.15 percent by weight. 20. Formable mixture as stated in claim 1, characterized in that it contains at least one ceramic clay. 21. 'Moldable mixture as specified in claim 20.', characterized in that the clay consists of Ifkaolin clay, sedimentary kaolin clay, ball clay, burnt clay or clay prepared for porcelain enamelling. 22.. Formable mixture as specified in claim 1, characterized in that the clay is present in an amount in the range from approximately 5 to approximately 40 percent by weight calculated on the total blading. 23. ; Formable mixture as specified in claim 1, lo a r, a k. t e r is t in that it includes fiberglass. 24. Formable mixture as set forth in claim 23, usable as press-sheet mixture 5, characterized in that it contains phenol formaldehyde condensate, Portland cement, gypsum cement, ball clay, ' zinc stearate and at least one silane bridging agent. .25 Moldable mixture as stated in claim 24, characterized by J&a) the molar ratio between formaldehyde and phenol is from approx. 1 to approx. 5 moles of formaldehyde per moles of phenol, (b) that water is present in an amount of from approx. 0.15 to approx. 5 moles of water per moles of formaldehyde, (c) that cement is present in a total amount of from approx. 1 to approx. 20 parts by weight per parts by weight of water, (d) that ball clay is present in an amount of from approx. 5 to approx. 40' parts by weight calculated on the pressure sheet Mandingen, (e) that glass fibers are present in a quantity that is greater than 0 and amounts to . to approximately 60 percent by weight calculated on the press sheet mixture, (f) that zinc stearate is present in an amount of up to approx. 5 percent by weight on the press sheet mixture, and (g) that the bridging agent is present in a total amount of up to approx. 5 percent by weight calculated on the press sheet mixture. 26. Formable mixture as stated in claim 24, kna r a c t e r i s e r t in that it includes 35.2 weight percent phenol formaldehyde condensate, 17.6 percent by weight Portland semefit, 17r 6 percent by weight gypsum cement, 14.0 percent by weight ball-clay, 14..0 percent by weight glass fibers5 1.4 percent by weight i-;ink stearate, 0.1 percent by weight gamma-aminopDopyltriethoxysilane and 0.1 weight percent tetraethoxysilane. 27.. Formable mixture as specified in claim 23, usable as a bulk forming mixture, characterized. In that it contains phenol formaldehyde condensate, Portland cement, gypsum cement, tule clay, glass fibre, zinc stearate and at least one silane bridging agent. 28. Formable blank as stated in claim 27, characterized in that the molar ratio between formaldehyde and phenol is from approx. 1 more. about. 5 moles of formaldehyde per mol f enol, (b) that water is present in an amount from approx. 0.15 to .;. 5 moles of water per moles of formaldehyde, (c) that cement is present in a total amount of from approx. 1 to 20 parts by weight of cement per parts by weight of water, (d>; that ball clays are present in an amount from approx. 5 to approx. 40% by weight calculated on the weight of the mixture (e) that glass fibers are present in an amount greater than 0 and up to approx. r60% by weight calculated on .the weight of the mixture, (f) that zinc stearate is present in an amount of up to about 5 weight percent calculated on the weight of the mixture and (g) that the bridging agent is present in a total amount of up to about 5 weight percent calculated on the weight of the mixture. 29. Formable mixture as specified in claim 27, characterized in that it comprises 36.2 weight-y-percent phenol formaldehyde condensate, 17.6 weight percent Portland cement, 17.6 weight pr. late gypsum cement, 14.0V ect percent ball clay,•14.0 weight percent glass fibers, 1 4 weight percent :-,ink stearate 0.1 weight percent gamma-aminopropyltriethoxysilane and 0£ weight percent tetraethoxysilane.