DE2155655C3 - Thermosetting molding compound - Google Patents

Description

30th

The invention relates to a thermosetting molding composition which is a vinyl chloride polymer, a reactive one Plasticizer, an unsaturated polyester resin, a polymerization initiator and an oxide or Contains hydroxide of beryllium, magnesium, strontium or barium or calcium hydroxide. The invention also relates to a foamable, thermosetting molding composition produced by the introduction of a bubble-forming material is obtained in the above-mentioned thermosetting molding composition.

The unsaturated ones used in the manufacture of fiber-reinforced plastics and as coating compounds Polyester resin compositions generally contain one of a saturated and an unsaturated dibasic Polyester derived from acid and a polyhydric alcohol and a monomer such as styrene Acrylic acid ester or an allyl alcohol ester.

Ice is known to harden these masses by putting in the Mass a polymerization initiator, e.g. B. an organic peroxide, introduced and the mixture thus obtained is heated or by adding a polymerization initiator and an accelerator, e.g. B. a metal salt the naphthenic acid, and the mass is then hardened at room temperature.

Articles made from such unsaturated polyester resin compositions in molds have the following Disadvantage:

1. The strong shrinkage during curing leads to deformation;

2. the objects are very hard but brittle;

3. the objects are flammable;

4. Ultraviolet radiation often leads to yellowing or damage;

5. Since the ester linkage in the polyester is easily hydrolyzable, the article has only one poor resistance to alkalis or boiling water;

6. thick parts tend to warp or to

Cracking because of the exothermic reaction when Hardening leads to violent heating:

7. Molding compositions that contain a polymerization initiator and / or an accelerator have only have a short pot life and are therefore difficult to process.

For the production of objects in forms from a vinyl chloride polymer, it is known in a Introduce a plasticizer for the production of paste vinyl chloride polymer powder and so to heat the obtained polyvinyl chloride plastisol.

For example, U.S. Patent Nos. 29 43 952 and 30 66 110, British Patent 594444 and Japanese Auslegeschrift 10 732/67 described a polyvinyl chloride plastisol that has a reactive plasticizer in the form of a lower aliphatic alcohol ester of acrylic or methacrylic acid also contains a vinyl chloride polymer and a non-reactive plasticizer.

In the USA. Patents 28 49 332 and 31 33 825 a polyvinyl chloride plastisol is described, the one reactive plasticizer in the form of a lower aliphatic alcohol ester of acrylic or methacrylic acid contains, as well as a vinyl monomer and a vinyl chloride polymer.

In U.S. Patent 29 18 736 are combinations of vinyl chloride polymer with an unreactive plasticizer and a vinyl monomer described.

When these plastisols are melted under the action of heat and converted into a gel, soft, elastic and extremely flexible products are obtained. These manufactured in molds However, products generally have the following disadvantages:

1. Very low hardness and low dimensional stability limit ';

2. The plastisol used as the starting material must melt and gel at high temperatures, e.g. B. over 180 ⁰ C, are heated;

3. poor resistance to oils and solvents;

4. poor resistance to staining;

5. a contact with the article manufactured in the mold or with the film Material becomes damaged or soft because of the plasticizer contained in the object or film exit.

It is used to manufacture rigid objects in molds or film from polyvinyl chloride plastisols also known to the amount of plasticizer required to produce a flowable plastisol reduce to a minimum, namely

a) by reducing the amount of plasticizer to a minimum;

b) through the use of a plasticizer that has a low viscosity and a low swelling effect on the vinyl chloride polymer, or

c) by introducing a suitable amount of relatively coarse resin particles into the vinyl chloride polymer.

However, the articles molded in this way or the film have one lower hardness than rigid vinyl chloride polymer products made from a vinyl chloride polymer without Plasticizer or with only a small amount of plasticizer by kneading with hot rollers or be made by extrusion.

For making objects using molds or for making films with greater hardness and solvent resistance. A higher softening point and a higher resistance to icing has already been suggested to use plasticizers, e.g. B. to replace oioctyl phthalate in whole or in part by a so-called reactive plasticizer, which has 1 to 3 double bonds in the molecule and which is made with a vinyl chloride polymer. z, R diallyl phthalate or ethylene glycol methacrylate, is compatible. whereupon a small amount of a radial chain polymerization initiator is added and the mass thus obtained is hardened under the action of heat. The films produced by this process or _{objects produced with the aid of 1S} molds, however, have a lower hardness and a lower softening point than the products made from the known unsaturated polyester resins. Compared to the usual rigid vinyl chloride polymer products, this mass has a lower conductivity, a much lower hardness and a much lower softening point. Furthermore, the reactive plasticizer used is expensive.

Attempts have already been made to use a small amount of an unsaturated polyester resin as a kind of reactive agent higen plasticizer to mix with a vinyl chloride polymer. For example, the Japanese describe Auslegeschriften 8659/64, 25795/64, 26276/54, 1550/66 and 10858/68 molding compounds made by mixing the reactive plasticizer in the form of an ester. z. B. a fumaric acid ester with the vinyl chloride polymer getting produced.

There are also molding compounds known that a contain unsaturated polyester resin, a vinyl chloride polymer and styrene (British patent 7 65 562 and French patent specification 15 10 442), as well as those containing an unsaturated polyester resin and a vinyl acetate polymer included (Japanese published publication 9269/67).

Compositions obtained by mixing an unsaturated polyester resin with the vinyl chloride polymer in any case have a high viscosity and poor compatibility. As they mix, the viscosity increases suddenly closes and a gel is formed. They are also very difficult to process or a coating from it because the masses only have a short pot life. Furthermore, the hardening of these Products obtained by the masses are opaque and brittle, which is very undesirable.

To overcome these drawbacks, various proposals have been made, e.g. B.

a) a process in which maleic anhydride and a glycol, e.g. B. butanediol, a low condensation Polyester resin formed and the terminal acid group with a monohydric alcohol is partially esterified (Japanese publication 1816/64).

b) a process in which a low-condensation polyester, made up of maleic acid and glycolic acid was formed, is modified with n-octanol (Japanese Auslegeschrift 11142/61) and

c) a process in which vinyl chloride polymer molecules are condensed with an unsaturated polyester (Japanese published publication 10712/65).

Each of these processes results in a low condensation, modified polyester resin. When these modified polyesters are introduced into polyvinyl chloride plastisols, the compositions obtained thereby can be processed into molded articles or into films which have great hardness. However, these polyvinyl chloride plastisols have the disadvantage that they harden more slowly on the surface when air is admitted than inside, so that the objects produced in this way in molds are brittle.

Since the masses mentioned are liquid, they can only are difficult to transport or manipulate and they tend to overflow from the during compression molding To form. The said masses also have the disadvantage that when they are heated during the Compression molding their viscosity is reduced, so that Vinyl chloride polymer contained in the masses! surfaces are precipitated and deposited. One can therefore no mold-made products with uniform mechanical strength properties receive.

If one introduces additives such as fillers or glass fibers into these masses, one takes place Deposition or precipitation of these additives as well as the vinyl chloride polymer. so that the products made in molds are often uneven.

The following processes are used for the production of display material products from thermosetting molding compounds bekan.it:

1. Before a molding compound hardens, a volatile substance is dissolved in it or becomes the Molding compound a blistering maierial added. A gas is then used for foaming. during the curing of the molding compound by gasification, thermal decomposition or a chemical reaction forms;

2. Before a molding compound is cured, a gas is introduced into it by stirring or the like and dispersed;

3. The measures specified under 1. and 2. above are combined with one another.

In heatable molding compounds, e.g. unsaturated polyester resins, bubbles have only a very small number of bubbles Stability. Over a period of several seconds to several minutes, the cells are forming Blisters compressed or destroyed. If you foam a molding compound and then harden it, the foams are compressed and destroyed before the mass forms a gel. It is therefore difficult to get one Pollutant product with a low density and to obtain fine, even pores.

Even if the curing is carried out immediately after the foaming of the unsaturated polyester resin it is very difficult to cure within a suitable time after foaming perform.

To avoid these disadvantages it has been proposed to use a thixotropic agent, e.g. B. cellulose acetal butyrate, to use. It is also already known to be an unsaturated polyester resin add acidic salt of a phosphoric acid ester with two carboxylic acid ester bonds (Japanese Auslcgeschrift 1520/64). It is also known for the production of foam products to use an anhydrous To produce a mixture that contains as main components a polymer and a substance that is suitable to form a gas upon contact with an acid, whereupon an aqueous emulsion is added (Japanese Interpretation document 2075/64). However, foam products cannot be made by these conventional procedures

with the required properties.

Unsaturated polyester resin products are easier to use when fine particles are added to them as fillers, such as a gas or a volatile liquid contain. These resin products are also sometimes referred to as foam products. In these products however, the fine particles are only embedded in the resin and are independent of each other and of each other present separately in their original state. On the other hand, there are no pole-like, continuous cells present. Therefore, when hardening such products, cracking easily occurs, warpage or breakage and the cured products have poor chemical resistance and weather resistance and they are easily flammable. It is because of these drawbacks that they are used limited

Compositions of a vinyl chloride polymer, a reactive plasticizer and an unsaturated one Polyester resin are liquid. Therefore, they cannot be easily transported or manipulated. Further they have the disadvantage that, due to their low viscosity, a gas escapes from the bubbles before the Curing is complete, so that the cells that have formed disappear and layers of cells exist flow together again. Therefore, a high expansion ratio cannot be obtained and are the Products uneven.

The low viscosity of the masses can be reduced to a certain extent by the use of larger ones Amounts of fillers, e.g. B. improve calcium carbonate, but the mechanical properties are so obtained foam products not satisfactory. When heating the masses of the above Kind to the curing temperature, the viscosity decreases very sharply, so that the evenly dispersed Vinyl chloride polymer and the pigment or other additives often deposit or settle. Information, meanwhile the foaming takes place unevenly and the mechanical properties vary in the Products.

When using a dispersible bubbling material a foam product with uniform cells cannot be obtained because of the bubbling material floats or settles

It is also already known for the production of cellular products to mix a rubber-like thermosetting material with a zeolite-like substance containing adsorbed gas and to heat the mixture so that the gas escapes from it (Japanese Auslegeschrift 1640/58). This process also does not result in foam products with uniform lines.

Recently, the above-mentioned, unsaturated polyester resins, polyvinyl chloride plastics and foamable molding materials Processes have been greatly improved, but also, as a result of the above, have the improved processes specified disadvantages only have a very limited area of application.

The main object of the invention is to create a thermosetting molding compound which consists of a vinyl chloride polymer, a reactive plasticizer, an unsaturated polyester resin, a polymerization initiator and an oxide or hydroxide of beryllium, magnesium, strontium or barium or calcium hydroxide

A thermosetting foamable composition consists of the above composition and a bubbling material incorporated therein.

The vinyl chloride polymer to be used in the molding composition according to the invention can consist of one Homopolymer of vinyl chloride or a mixed

S polymer of vinyl chloride with another, so that copolymerizable monomers exist. Included it can be copolymers of vinyl chlorid with vinyl acetate vinyl propionate methyl methacrylate, Butyl acrylate vinylidene chloride, acrylonitrile, vinyl ether,

ίο diethyl maleate acrylic acid. Methacrylic acid or maleic anhydride Act. The vinyl chloride polymer may further comprise a saponification product Copolymer of vinyl chloride and vinyl acetate exist.

To produce moldings with excellent physical properties, the homopolymer must or the copolymer of vinyl chloride has a high degree of polymerization. In general a homopolymer or a copolymer of vinyl chloride is preferably used a degree of polymerization of 500 to 2500. The average grain size of the vinyl chloride polymer is preferably 0.05 to 50 μm, in particular 0.2 to 2 μm, in particular a homopolymer of vinyl chloride or a copolymer of vinyl chloride containing 95 to 99 percent by weight vinyl chloride used with vinyl acetate as it is used for pastes. To form a Plasüsol with a low viscosity can be a coarse-grained vinyl chloride polymer with a grain size of 5 to 100 µm as an extender together with the homopolymer or copolymer of vinyl chloride mentioned use.

The vinyl chloride polymer is preferably based on in an amount of 5 to 60 percent by weight the total mass used when using less than 5 percent by weight of vinyl chloride polymer The product does not have the desired flexibility and flame resistance of more than 60 percent by weight, the mass has too high a viscosity and not a good one Processability Furthermore, this lowers the dimensional stability limit of the product so that ss in the Practice cannot be used.

The one used in the composition of the invention reactive plasticizer is an acrylic acid ester plasticizer with the general formula

CH ₂ -C -C- O A QCC =

in which A is a residue of a compound m at least two hydroxyl groups on the Moteküleodcn, or a compound which contains at least one ester or ether bond and at least two terminal hydroxyl groups in the molecule, X is a hydrogen or halogen atom or an alkyl group, e.g. R. is a methyl or ethyl group, and π and m are integers from 1 to 3.

Examples of the reactive plasticizer are

Ethylengiykokiimethacrvlat 6s propylene glycol acrylate,

13-Bmandk> kimethacrylat 1,4-butanediol dimethacrylate. 23-Butanedioklniicthacrviai

2-Ethy! -1, 3-hexanediol dimethyl acrylate.

I.S-pentanediol dimethacrylate.

1,6-hexanediol dimethacrylate,

Neopentyl glycol dimethacrylate.

Glycerine urimethacrylate.

Dimethacryl (bisdiethylene glycol) phthalate,

Dimethacryldi (bisethylene glycol) phthalate,

Dimethacrylic (bisethylene glycol) maleate,

Tetramethacryl (bisglycerin) phthalate,

Triethylene glycol dimethacrylate,

Telramethylene glycol dimethacrylate,

Polyethylene glycol dimethacrylate and

Trimethylolpropane trimethacrylate.
One can also use allyl-containing reactive plasticizers, e.g. B.

Allyl acrylate,

Triallyl cyanurate.

Diallyl maleate,

Diallylitaconate,

Diallylsebacate,

Diallyladipate,

Diallyl glycolate,

Triallylaconitate,

Diallyl monooctyl phosphate,

Triallyl phosphate,

Diallyl isophthalate and

Diallyl benzene phosphate.

It is also possible to use alkyl esters of non-acidified substances Use acids in which the alkyl radical preferably contains 4 to 16 carbon atoms, e.g. B.

Dibutyl maleate,

Dicyclohexyl maleate.

Dioctyl maleate

Dibutyl fumarate.

Dicyclohexyl fumarate.

Dioctyl fumarate,

Dibutyl itaconate,

Dioctyitaconate,

Cyclohexyl acrylate,

Octyl acrylate,

Lauryl acrylate,

Caprylic acrylate.

Cyclohexyl methacrylate,

Octyl methacrylate

Lauryl methacrylate and

Caprylic methacrylate.

These reactive plasticizers can also be used in combination with one another.

The content of the reactive plasticizer in the composition according to the invention is at most 60 percent by weight and preferably at least 2 percent by weight for a composition which is free from the non-reactive plasticizer, and at most for a composition which, in addition to the reactive plasticizer, contains an non-reactive plasticizer and / or a vinyl monomer 50 percent by weight, preferably at least 2 percent by weight. By using the reactive plasticizer in an amount of more than 60 or 50 percent by weight, the shelf life of the mass is reduced and the mechanical properties of the product are not improved

Part of the reactive plasticizer can be replaced by a non-reactive plasticizer. This replacement leads to several advantages. For example, the hardening rate can be adjusted in this way and the temperature of the exothermic reaction can be controlled in the desired manner, so that the formation of cracks can be prevented in molds in the production of complexly shaped objects. You can also improve the impact strength of the product in this way.
As the unsaturated polyester resin in the composition according to the invention, one of the commercially available unsaturated polyester resins known for the production of molded articles, cladding panels, laminated panels, coatings and the like can be used.
ίο In general, some of the unsaturated dibasic acid is replaced by a saturated aliphatic or aromatic dibasic acid, e.g. B. by adipic acid, sebacic acid, phthalic anhydride, iso phthalic acid. Terephthalic acid and chlorinated phthalic acid.

As polyhydric alcohols, for example
Ethylene glycol,
Diethylene glycol,
Propylene glycol,
Dipropylene glycol,

1,6-hexanediol,
1,3-butanediol,
2,3-butanediol,
Neopentyl glycol,
2s hydrogenated 2,2'-bis (4'-oxyphenyl) propane and

2,2-di (4-oxypropoxyphenyl) propane
use.

Within the scope of the invention is used ah polyhydric alcohol preferably Neopentylglyko} o alone or in combination with ethylene glycol, Diäthy glycol, propylene glycol, dipropylene Odei 1,6-hexanediol. In this case, the hydric alcohol component preferably contains at least 30 mole percent neopentyl glycol. Furthermore, it is preferred to use 1,6-hexanediol or a combination of at least 30 mol percent 1,6-hexanediol. The remainder of at least one of the following other polyhydric alcohols: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and neopentyl glycol. By using such a combination of polyhydric alcohols, the compatibility of the unsaturated polyester resin, de; Vinyl chloride polymer, the vinyl monomer and de; reactive plasticizer with each other improve; and obtain a composition whose viscosity does not change even with the passage of time, so that the composition has a very long shelf life.

In the drawings, F i g. 1 in a plan view

partially cut away, a foam product, there; by introducing a mass according to the invention ir a round shape and foaming the mass untei

Exposure to heat was generated.

F i g. Fig. 2 shows a vertical, partially cut away section along the line IMI in FIG. 1. F i g. 3 shows in a graph the change in the thixotropic properties of masses, soft eir Vinyl chloride polymer a reactive plasticizer a vinyl monomer and unsaturated polyester resins contain, depending on the mole fraction de; Neopentyl glycol in the total amount of polyvalent gen alcohols.

The F i g. 3 shows the course of the viscosity in front of masses containing an unsaturated polyester resin, eir Vinyl chloride polymer contain a vinyl monomer and a reactive plasticizer.

Curve A shows the viscosity profile of a compound which, in a mixture, contains an unsaturated polyester hane which is produced by a reaction of one mole of phthalic acid.

609 636/180

ίο

anhydride, one mole of maleic anhydride and 2.2 moles of polyhydric alcohols.

Curve B shows the viscosity profile of a compound which contains in a mixture an unsaturated polyester resin which was produced by a reaction of one mole of isophthalic acid, one mole of maleic anhydride and 2.2 moles of polyhydric alcohols.

The polyhydric alcohols used were neopentyl glycol (NPG) and propylene glycol (PG); with the NPG content changed.

From the figure it is clearly shown that the compositions thixotropic properties (after 5 days of storage at 25 ° C), because the Brookfield Viskome- ter a ratio of 4 U / min (Vi) and 20 U / min (V20) measures.

The unsaturated polyester resin suitably has an average degree of condensation of at least 4 and a number average molecular weight of 1,000 or more. The use of an unsaturated polyester resin with a molecular weight below 1000 results in a cured product with poor mechanical properties. The numerical average molecular weight is determined with the help of an ebulliometer according to the ebullioscopic method.

The unsaturated polyester resin is preferably used in the composition of the present invention in an amount of 5 to 60 weight percent used. An amount less than 5 percent by weight will reduce the mechanical Strength not improved. If it is more than 60 percent by weight, it is difficult to get enough To obtain flowable mass, and the end product has a low mechanical strength.

It is special when the composition according to the invention is used to produce a foamable composition advantageous to use an unsaturated polyester resin which can be synthesized using the Isophthalic acid was produced as the unsaturated dibasic acid. This leads to advantages with regard to the foaming ratio, the uniformity of the cells and the reproducibility of the Foaming. Unsaturated ones made using other unsaturated dibasic acids Polyester resins are less suitable from these points of view.

The polymerization initiator used in the present invention can be made of, for example, an organic Peroxide, like

Acyl peroxide,

Methyl ethyl ketone peroxide,

Lauroyl peroxide, Benzoyl peroxide,

tert-butyl perbenzoate,

Di-tert-butyl peroxide, Oxycyclohexyl hydroperoxide and Cumene hydroperoxide

consist, or an azo type catalyst, e.g. B. ", Tf'-azobisisobutyronitrile. These polymerization initiators can also be used in combination with one another be used.

The composition according to the invention contains beryllium oxide, magnesium oxide, strontium oxide, barium oxide or beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide as an essential component of the invention.

The above-mentioned oxides or hydroxides are contained in the composition according to the invention in an amount of 0.1 to 10 percent by weight. If the component is used in an amount of more than 10 percent by weight, the processability of the mass and the mechanical strength of the end product are reduced.

The effect is mainly based on the cations of these metals. In particular, these metals are using Anions of the polyvinyl chloride or of the unsaturated polyester resin bound, whereby there is a structure, which is networked at room temperature, but at

ίο Temperatures nearly as high as that Deformation temperature when deforming in a form that becomes flowable, but such a viscosity possesses that it remains stable under a suitable pressure, so that the mass easily processed in a mold

is can be.

The compounds indicated above are particularly suitable for improving the flowable wedge the mass at high temperatures.

These compounds are therefore referred to below as "thickeners".

There are so far no publications known which the use of the thickener in a Describe mass, the unsaturated polyester resin, the vinyl chloride polymer and the reactive Contains plasticizers.

The use of the thickener reduces the tendency for the Particles of the vinyl chloride polymer, the blistering material or eliminated by reinforcing agents,

w so that very uniform products are always obtained.

These properties are very important for the in

Molded or foamed products.

the uniform mechanical strength properties

or have a uniform foaming ratio

J5 should.

The blistering material used in the invention consists of fine particles that form a gas. a low-boiling liquid or a slightly gas containing solid forming. It is important that these fine particles are kept at a temperature below the Give off a gas at the gel formation point of the composition according to the invention. The fine particles can, for example consist of resinous substances, e.g. B. from phenol, epoxy. Polyethylene, polyurethane, polypropylene. Polystyrene, polyacrylic, polyester, polybutadiene, polyamide. Polyisoprene, silicone, and cellulose resin. also from gelatine, polyvinyl alcohol, vinyl chloride-ethylene copolymers and inorganic substances, like glass.

The gas contained in the fine particles can, for example, be made from an inert gas such as helium, neon or argon, or from an incombustible gas such as air. Nitrogen, carbon dioxide, ammonia gas, ethane, propane. Butane or halogenated hydrocarbons exist. The liquid contained in the fine particles can for example consist of a saturated hydrocarbon such as pentane, hexane or heptane, or a low-boiling solvent or a liquid such as petroleum ether, benzene, carbon tetrachloride or water.

? ^{it contained in de} n fine particles, easily a gas forming solid can for example consist of an inorganic compound which decomposes when heated to give off a gas, z. B. from ammonium carbonate and sodium bicarbonate or from an azo compound such as dinitrosopentamethylenetetramine. Azobisisobutyronitrile, toluenesulfonylhydrazide derivatives and p-toluenesulfonazide. as well as subliminal

capable substances such as camphor or naphthalene. Examples of blistering materials are given below:

(1) Made of glass or a resin-like substance, fine hollow particles with a grain size of 5 μτη tys 2 mm, which contain an inert gas, an incombustible gas or a lower saturated hydrocarbon, e.g. B. glass microballoons, "shirasu glass" microballoons, perlite microballoons, phenolic resin microballoons and butane-containing polystyrene beads;

(2) Microcapsules made of a resin-like substance, which are a solid or a Contain liquid, one of the above

specified, low-boiling compounds, azo compounds or substances capable of sublimation, or a mixture of such solids and liquids, optionally with a small one Amount of gas;

(3) particles of molecular sieve-like adsorbents, those for selectively adsorbing a large amount of the above inert gas, incombustible Gas, lower saturated hydrocarbon or the low-boiling liquid suitable are e.g. B. zeolite.

The table below shows physical properties of glass microballoons listed under (1) and »Shirasuglas« microballoons:

“Shirasuglasw microballoons Commercial glass Microballoons Look white to faint White dust brownish powder composition Aluminum silicate Sodium borosilicate Bulk density 0.33 to 0.67 0.33 density 0.14 to 0.32 0.22 Grain size range (μιτι) 30 to 600 10 to 250 Average grain size (μΐη) - 65 Grain wall thickness (μΐη) 6 to 14 2 Softening point (° C) 900 to 1000 480 Melting point (° C) 1200 to 1300 760 Thermal conductivity (kcal / mh ⁰ C) 0.07 0.056 Hygroscopicity (% in 24 h) 0.08 2.8

The manufacture of the »Shirasu glass« microballoons is described in Engineering Materials (Kogyo Zairo), Volume 19, No. 8, Pp. 84 to 89 are described in detail.

Blistering materials can be used in the composition according to the invention of the types indicated by (1), (2) and (3) above. Given the Expansion ratio, the uniformity of the pile-shaped pores in the product and the reproducibility of the foaming process, however, the blistering materials are designated by (1) Type most preferred because the bubbling materials of the types denoted by (2) and (3) are shown in the points mentioned are somewhat inferior to those of type (1).

The blistering material is used in the composition of the present invention in an amount of 1 to 50% Weight percent, preferably 5 to 30 weight percent, is used

The vinyl monomer and / or the non-reactive plasticizer are used in the composition of the present invention optionally used

The vinyl monomer used in the invention can consist of the monomers which have at least one double formation in the molecule. Examples of these monomers are styrene and vinyl acetate Methyl methacrylate, butyl acrylate, chlorostyrene, divinylbenzene and acrylonitrile.

The vinyl monomer is added to the mass adjust their viscosity and the hardness, chemical resistance and mechanical properties of the foam product obtained.

The vinyl monomer is used in an amount of at most 40 weight percent and preferably at least 2 percent by weight used. When using the vinyl monomer in an amount greater than: Percent by weight, the foam end product has a high volume shrinkage, so that cracking and ( Distortions occur.

As non-reactive plasticizers, all customary non-reactive plasticizers for polyvinyl chloride can be used, e.g. B. phthalic acid esters such as dibutyl phthalate
Diamyl phthalate

Dimethoxyethyl phthalate,

Dibutoxyethyl phthalate
Dicyclohexyl phthalate
Dihexyl phthalate
Diheptyl phthalate
Butyl octyl phthalate

Di (n-octyl) phthalate Di (2-ethylhexyl) phthalate Diisooctyl phthalate Didecyl phthalate, Didodecyl phthalate and

Butyl benzyl phthalate;

also phosphates, such as Alkyldiphenylphosphhal ur Tricresylphosphat and others unresponsive Plasticizers such as dicapryl, didecyl and di-2-äthylh xylester of adipic acid, succinic acid, azelaic acid and sebacic acid. In combination with the protruding For example, the non-reactive softeners listed can be conventional plasticisers from the pole ester and epoxy types are used for common vinyl chloride polymers and chlorinated paraffin Preferably, plasticizers are used because of the fluidity and shelf life of the poly Do not affect the nyl chloride plastisols. You ka

also use mixtures of two or more of these plasticizers.

The non-reactive plasticizer is in the composition according to the invention in an amount of at most 50 weight percent and preferably 5 to 50 weight percent used when using the reactive plasticizer in an amount not exceeding 50 percent by weight can improve the flowability and the viscosity of those consisting of the unsaturated polyester resin and the vinyl chloride polymer Improve mass, influence the hardening speed of the mass and the flexibility of the in one Improve the shape of the manufactured item. In the case of an amount of more than 50 percent by weight, one obtains a brittle product with poor mechanical properties.

By using the non-reactive plasticizer in the composition according to the invention, adjusted the viscosity of the mass, influenced the temperature of the exothermic reaction during curing and the flexibility of the article manufactured in a mold can be improved.

Below are examples of compositions of thermosetting compositions according to the invention indicated, which consists of a vinyl chloride polymer, an unsaturated polyester resin, a reactive Plasticizer, a non-reactive plasticizer, a vinyl monomer, a polymerization initiator, a thickening agent and a blistering material can consist of:

(I) Molding compositions according to the invention without blistering material:

(1) heatable molding compound containing 5 to 60 percent by weight of vinyl chloride polymer, 5 to 60 percent by weight unsaturated polyester resin, no more than 60 percent by weight reactive plasticizer, 0.1 to 10 percent by weight thickener and 0.2 to 3 percent by weight polymerization initiator contains;

(2) heatable molding compound as specified in (1), but with the reactive plasticizer in an amount not exceeding 50 percent by weight and an unreactive plasticizer in one Amounts not exceeding 50 percent by weight are used;

(3) Thermosetting molding compound as specified in (1), but with the reactive plasticizer in in an amount not exceeding 50 percent by weight and a vinyl monomer in an amount of no more than 40 percent by weight are used;

(4) Thermosetting molding composition as specified in (2), but with a vinyl monomire in an amount at most 40 percent by weight is used.

(H) Molding compound with blistering material:

(1) foamable, thermosetting molding compound containing 5 to 60 percent by weight vinyl chloride polymer, 5 up to 60 percent by weight unsaturated polyester resin, at most 60 percent by weight reactive Plasticizer, 0.1 to 10 percent by weight, thickener, 0.2 to 3 percent by weight Polymerization initiator and 1 to 50 weight percent bubbling material.

(2) Foamable, thermosetting molding compound as specified in (1), but with the reactive Plasticizers in an amount of at most 50 percent by weight and less reactive Plasticizers are used in an amount not exceeding 50 percent by weight.

(3) foamable, thermosetting molding compound as in

(1), but with the reactive plasticizer in an amount of not more than 50 % By weight and a vinyl monomer in an amount not exceeding 40% by weight will be

(4) foamable, thermosetting molding compound as in

(2), but with a vinyl monomer in an amount not exceeding 40 percent by weight is used.

If in the masses (l) - (3), (I) - (4). (H) - {3) and (Il) - (4) the proportion of vinyl monomer exceeds 40 percent by weight is the temperature of the exothermic reaction too high during curing and therefore the volume shrinkage too great, so that it leads to deformation In addition, the product then obtained has only low mechanical strength and chemical strength Resistance.

If in the masses (I) - (2), (I) - {4), (H) - (2) and (II) - (4) the proportion of non-reactive plasticizer exceeds 50 percent by weight, the hardness, the chemical resistance and other properties of the final product deteriorated.

The main components of the composition according to the invention can be mixed with one another, for example, as follows will:

(1) You can vinyl chloride polymer in a known manner with the reactive plasticizer or mix a mixture of the reactive with the non-reactive plasticizer and the polyvinyl chloride plastisol thus obtained

(a) a solution of the unsaturated polyester resin in the reactive plasticizer,

(b) a solution of the unsaturated polyester resin in the vinyl monomer or

(c) A mixed solution of the unsaturated polyester resin, the reactive plasticizer and the Mix in vinyl monomers.

(2) You can use a vinyl chloride polymer directly in

(a) a solution of the unsaturated polyester in the reactive plasticizer,

(b) a solution of the unsaturated polyester resin in the vinyl monomer or

(c) a mixture of the unsaturated polyester resin, the reactive plasticizer and the Bring in vinyl monomers.

To improve the shelf life of the mass, e.g. B. to prevent an increase in viscosity during storage, the vinyl chloride polymer is preferably mixed with the reactive plasticizer or the non-reactive plasticizer or a mixture thereof, so that the particles of the Vinyl chloride polymer powder are coated with the plasticizer, whereupon the coated powder with the unsaturated polyester resin solution containing the vinyl monomer and the other ingredients contains. In this way you can direct contact of the vinyl chloride polymer with the Avoid vinyl monomers, which have a relatively high resolving power, so that the vinyl chloride polymer does not dissolve and does not swell on storage and the mass has excellent storage stability has.

The polymerization initiator, the bubbling material and the thickener are added to the

! a mixture mixed evenly. The composition obtained in this way is generally cured at 60 to 180 ^° C. and under a pressure of from 0 to 300 kp / cm ² for a period of from 10 seconds to 1 hour. As a result of the curing, the reactive plasticizer and the unsaturated polyester are crosslinked independently and mutually, so that the gel made from the vinyl chloride polymer or the non-reactive plasticizer is held in place by the network structure formed and the hardness and strength of the cured product can be increased.

The above effect is also observed in the mass containing the bubbling material. Even at a relatively low curing temperature of, for example, about 120 ^° C., the unsaturated polyester resin, the reactive plasticizer and the vinyl monomer are crosslinked. The internal temperature of the molded mass is increased by the heat of polymerization generated upon curing, so that curing takes place in a very short time even if a cured product of a very large thickness is produced.

Simultaneously occurs due to the melting or decomposition of the bubbling material or the Desorption of the adsorbed gas is the discharge of the gas. In the mass according to the invention there is a large one The amount of heat of polymerization stored in the core of the mass located in a mold. In this core the mass in the mold is therefore melted or the bubble-forming material decomposes and the release of the gas before the mass is crosslinked, so that a layer of pile-like, continuous cells with a diameter of 0.5 to 20 mm is formed.

In a surface layer with a depth of up to Several millimeters from the surface, crosslinking and hardening take place before melting or the decomposition of the bubbling material so that insufficient gas is given off, a formation of prevents pile-like continuous cells and a dense, even surface layer with a low expansion ratio is formed. For this foaming process, the molding compound should on the one hand have such a high flowability that it does not hinder foaming during curing, and on the other hand such a high viscosity that cells formed do not break from surrounding them Resin film are destroyed.

The following is the foaming and curing of the molding compound containing the bubble forming material described according to the invention with reference to the drawings.

(1) The composition of the invention is first introduced into a suitable mold and heated to a temperature of 50 to 18O ⁰ C. The part of the mass that is in direct contact with the mold is heated quickly and hardened by the crosslinking reaction. In this part, the hardening takes place faster than the decomposition and melting of the bubbling material and the release of the gas. As a result, the mass is hardened and the formation of bubbles is prevented. In this way, a dense surface layer 1 with a low expansion ratio is formed.

(2) In the inner part of the molded mass that is in direct contact with the mold, it becomes gradually heated by heat transfer so that it has high fluidity. Takes place at the same time

due to the heating of the bubbling material, gas is released and bubbles are formed.

(3) Vinyl chloride polymer particles are also heated so that they coexist with the reactive Plasticizer, the non-reactive plasticizer or the vinyl monomer swell or soften or melt and the mass adopts a high viscosity. Therefore, the biases are not destroyed and don't go away. The bubbles move upwards to form hollow, pile-shaped pores 2.

(4) The crosslinking reaction then takes place in the highly viscous molding compound which contains the pile-shaped pores 2, so that the molding compound retains its flowability loses and is hardened in this state. Therefore, the bubbles remain in the molding compound.

In the above-mentioned foaming and hardening process, the foaming ratio can be determined by the Presence of a suitable amount of a volatile liquid, e.g. B. the vinyl monomer or one ordinary solvent. This volatile liquid becomes during foaming and curing heated to their boiling point. In this state, it is believed that the bubbling material acts in a similar way to a zeolite in an ordinary, boiling liquid, i. that is, it's gassing promotes the volatile liquid and thereby the amount of gas available for foaming enlarged.

However, common solvents condense and remain in the foam product after foaming, whereby the mechanical properties of the product are deteriorated and an unpleasant one Odor is caused. For this reason, the use of common solvents is not possible preferred, but the vinyl monomers are preferred in bulk, because they do not: to the lead to specified disadvantages.

In ordinary unsaturated polyester resins or diallyl phthalate polymers that are derived from the vinyl chloride polymer are free, one can find a suitable fluidity and a match between the pro Time unit delivered amount of gas and the speed of the crosslinking reaction do not achieve, so that in this way, it is not possible to obtain a foam product which has a high expansion ratio and is pole-shaped Owns cells.

The usual polyvinyl chloride plastisols have to be ^{heated to temperatures above 180 °} C. for curing and foaming, and in fact for a very long time in the production of thick objects in molds so that the core of the mass melts.

In the composition according to the invention, the unsaturated polyester resins polymerize in the presence of reactive plasticizers or vinyl monomers even at a relatively low temperature of ζ. Β 60 to 180 ° C and causes the polymerisa tion reaction generated heat a warming de; Core of the mass in the form. The in dei Plasticizers or vinyl monomers contained in the mass

do ren support the melting of the vinyl chloride po lymerisates and improve its processability. Tue < The mass according to the invention can therefore also be used when producing a thick object in a form i be melted and hardened in a short time.

(λ Furthermore, there is / is a difference from the ordinary unsaturated polyester resins when hardening de composition according to the invention in a form none violently Heat build-up. so that a strong Schrumr

development, shrinkage deformation and cracking | L the like can be avoided.

The advantages of the molding compound according to the invention and (anything produced therefrom with the aid of molds pes compared to the usual unsaturated polyester resins and vinyl chloride polymers The objects made from it with the help of molds are briefly summarized below:

1. Since the mass is in a semi-gel-like, putty-like state, it can be very easily manipulated and packaged.

2. Since it is in a semi-gel state, it does not find any during storage Separation and no settling of resin, is Pigment, reinforcement material and other additives take place and the quality of the mass remains constant.

3. When deforming in matching metal molds, the mass becomes good when heated flowable. There is no uneven coloring. The mass can be excellent in forms are processed.

4. During deformation in a mold, the mass has a lower volume shrinkage than that common unsaturated polyester resins.

5. The exothermic reaction during curing is milder than with the usual unsaturated polyester resins.

6. The gel formation and curing of the molding compound can take place at lower temperatures than with the usual polyvinyl chloride plastisols.

7. The products cured in molds have excellent mechanical properties, e.g. B. Hardness and elasticity, and excellent chemical properties, such as heat resistance, water-is water resistance, chemical resistance wedge, weather resistance and resistance to stains.

8. The cured products are not so easily flammable and have excellent flame resistance.

9. The cured products have a specific cell structure with a dense surface layer and an inner layer of pile-like, continuous cells.

As a result of this specific structure, they have a low density and a high dimensional stability limit as well as excellent mechanical properties.

Reinforcing materials, fillers, stabilizers, Add pigments, dyes, lubricants, lubricants and other additives.

The mass according to the invention can above all with the aid of molds made of complementary metal parts or in the transfer molding process, in the injection molding process and! processed by casting. One can on in this way to produce films, foils, cast products, multilayer panels as well as reinforced ones Composite body made of a plastic to which glass fibers or the like are admixed. Own all of these products fine high dimensional stability limit and excellent do | e mechanical properties.

Attempts have been made to manufacture reinforced plastics in molds to achieve a higher level Mechanize profitability. For example, Is is known, for this purpose a molding compound in the form of f> s liner foil or bulk material to be used. The mass according to the invention is for use in Very suitable in such a process.

In particular, the composition according to the invention is suitable in contrast to the usual molding composition in Form of a film for deep drawing. The usual molding compound in the form of a bulk material is that according to the invention Superior to mass, because the products made from it in molds are excellent Dimensional accuracy when hardening and have a smooth surface.

One can produce products with a smooth surface by thermoforming or with the help of molding Manufacture injection molding presses because the viscosity of the mass can be easily influenced and the mass has excellent flowability when exposed to heat before fully hardening.

As a result of its low volume shrinkage, the composition according to the invention is particularly suitable for compression molding. K-ian can use reinforcing materials such as glass fibers, asbestos, carbon fibers, boron fibers, metal fibers, synthetic fibers and natural fibers in the composition according to the invention. These reinforcing materials hardly appear on the surface of the molded article, and molded articles can thus be used to produce excellent dimensional stability and substantially free from cracks or warpage.

Multi-layer objects can also be produced from the composition according to the invention with the aid of molds will. For this purpose, the reinforcement materials mentioned above can be used with the Impregnate mass according to the invention and then wrap around a mandrel so that on this one Laminated body of the desired thickness is produced, whereupon the laminated body under the action of heat cured and the cured laminate is optionally separated from the mold core. at This production of multi-layer products can be done in such a way that the first layer is the Thickening agent and the second layer overlying the first layer the blistering material and the third layer overlying the second layer has the same composition as the first Layer. If you then heat and cure this multilayered arrangement, you get a multilayered one Composite body in which a foam layer between non-foamed layers is arranged. It is also possible to produce sound-absorbing and heat-insulating composite laminate panels, by laying on a substrate plate, e.g. B. made of plywood, hardboard, chipboard, chipboard, Asbestos plate or slate plate forms a coating from the composition according to the invention and this coating hardens under the action of heat.

Since the composition according to the invention is a vinyl chloride polymer containing thermosetting bafe resin, the main component of which is the unsaturated polyester resin is formed, can be made from the composition of the invention with each other or with objects other objects made of known vinyl chloride polymers stick together because the vinyl chloride polymers are thermoplastic and adhesive when molten. In particular, it causes heating of the vinyl chloride polymer molecules in the vicinity of the interface to be bonded, that these molecules melt and diffuse, whereby they have an adhesive effect. You get a good one that way Adhesive connection between two objects from the semi-gel-like mass or between the one from the mass

existing object and the object made of the known vinyl chloride polymer. Such a one An adhesive bond can also be established between cured objects.

pie invention is referred to below with reference to Examples are described, all percentages and parts being on a weight basis unless nothing other is stated.

example 1

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester, non-reactive Plasticizers, vinyl monomers, polymerization initiators and thickeners.

A four-necked flask, which had a capacity of 2 liters and was provided with a stirrer, a thermometer, a reflux condenser (with a device for measuring the water content) and a tube for introducing nitrogen gas, was _{filled with I 1} IMoI of neopentyl glycol, 0.4 mol of isophthalic acid and Oi mol of maleic anhydride charged. These components were reacted for 4 hours under a nitrogen gas atmosphere at 150 to 18O ⁰ C and further 4 hours at 200 to 220 ° C, wherein the water formed in the reaction was removed. In this way, an unsaturated polyester resin A having an acid value of 16, number average molecular weight 1340 and average degree of condensation 13. 40% styrene and 0.01% hydroquinone were added to the unsaturated polyester resin A and dissolved in the resin, one being unsaturated Polyester resin solution AI was formed, the weight of which the percentages are based.

Separately, a polyvinyl chloride plastisol (a) was produced by adding 100 parts of a vinyl chloride polymer for the production of Pas'e, with an average degree of polymerization 1650, with 30 parts of di (2-ethylhexyl) phthalate and 30 parts of ethylene glycol dimethacrylate mixed and a Poiymerisationsinitiator in the mixture and a stabilizer for vinyl chloride polymer was introduced. The mixture was under degassed under a negative pressure.

After 2% magnesium oxide and 1% benzoyl peroxide had been added to a mixture of the unsaturated polyester resin solution AI and the polyvinyl chloride plastisol (a), the mixture was mixed thoroughly with the aid of a mixer and was ^{heated to 50 °} C. for 1 hour. The mixture lost its flowability and a semi-gel-like solid with poor adhesiveness was obtained (sample no. 1 from the composition according to the invention). Control masses (Sample Nos. 2 to 5) were prepared in the same way. Results of tests to which these sample masses were subjected are given in Table 1.

The mass according to the invention has only low adhesiveness and can easily be in the form of a block be manipulated. Furthermore, in the invention The mass of the vinyl chloride polymer is not deposited during storage and curing, and an article made thereon in a mold had low volume shrinkage and good Dimensional accuracy and was self-extinguishing.

Table 1

Sample # 1

composition

Unsaturated polyester resin solution AI
Polyvinyl chloride plastisol (a)
Vinyl chloride polymer for paste
Di (2-ethylhexyl) phthalate
Ethylene glycol dimethacrylate

Stabilizer composition for vinyl chloride polymer (Zn / Cd / Ba type)

Magnesium oxide
Benzoyl peroxide

properties

Condition in the container

Cast products (heated to 120 ° C for 20 minutes) Appearance

Volume shrinkage,%

Hardness (Rockwell R)

Ball drop test for impact strength

Flame resistance

200 200 100 200 200 200 100 100 _ 100 100 100 30th 30th - - 60 30th 30th 30th - - - 30th 3 3 3 3 3 7.2 - 2 - - - 3.6 3.6 1 3 3.6 3.6 A. B. A. C. D. E. F. F. G H 1 F. K K K L. L. M. 4.5 4.5 9.1 - - - 125 124 129 121 91 124 N - O O O M. P. - 0

Of the samples given in Table 1, sample no. 1 consisted of the sample according to the invention Dimensions. Samples 2 through 5 were control samples.

The ossified product consisted of a disc 50 mm in diameter and 5 mm thick.

For the ball drop test, a steel ball of 100 g was placed on the test specimen from a height of 50 cm dropped (according to JlS K-6745).

The properties are indicated by the letters A to 1 as follows:

A semi-gel-like solid with little clingability

good flowable liquid

sharp increase in viscosity and rapid settling of the vinyl chloride polymer
sharp increase in viscosity and settling of the vinyl chloride polymer at medium speed

slight increase in viscosity and slow settling of the vinyl chloride polymer
well cured

Cracks, warps and twists
Warping
uneven curing
Well

opaque and cloudy
transparent
unchanged
destroyed
self-extinguishing
easily flammable

Example 2

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomers, non-reactive plasticizer, polymerisation initiator and thickener

In the same reaction vessel as in Example 1, 0.6 mol of propylene glycol, 0.5 mol of neopentyl glycol, 0.5 mol of dimethyl terephthalate and 0.5 mol of maleic anhydride reacted. When the reaction product the acid number reached 15, it was cooled. An unsaturated polyester resin B was obtained with the number average molecular weight 1350 and the average degree of condensation 14. 40% styrene and 0.01% hydroquinone were added to the unsaturated polyester resin, one being unsaturated Polyester resin solution B-I was obtained, to which the percentages are based.

Separately, a polyvinyl chloride plastisol (b) was prepared by adding 100 parts of a vinyl chloride polymer for paste with 40 parts of di (2-ethylhexyl) phthalate, 60 parts of tetraethylene glycol dimethyl acrylate and 3 parts of a stabilizer mixture (Zn / Cd / Ba type) introduced and the mixture under one Vacuum was degassed.

When mixing 203 parts of the plastisol (b) with 50 parts of the unsaturated polyester resin solution BI. 2.5 parts of benzoyl peroxide and 5 parts of beryllium oxide increased in viscosity even at room temperature and a semi-gel-like solid with poor tackiness was obtained 24 hours after mixing (sample No. 7). The heating of this sample to 120 ^° C. for a period of 20 minutes in a mold

Table 2

resulted in a product which, like the molded article obtained from Sample No. 1 of Example 1, has a excellent ϊ had dimensional stability and an excellent appearance. The product was also excellent physical properties and high flame resistance and a small volume shrinkage.

Example 3

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomer, Polymerization initiator and thickener

For producing a polyvinyl chloride plasma isolator (c) were 100 parts of a vinyl chloride polymer powder (average degree of polymerization 1700) with 60 parts of trimethylolpropane trimetha.crylate and 3 parts of a stabilizer mixture for vinyl chloride polymer mixed and the mixture was kneaded so that the additives were dispersed in the polyvinyl chloride.

Separately from this, 1.1 mol of 1,6-hexanediol were placed in the reaction vessel also used in Example 1. 0.5 mol of isophthalic acid and 0.5 mol of maleic anhydride reversed. An unsaturated polyester resin was obtained C with the acid value 15, the number average molecular weight 1440 and the average degree of condensation 13. This unsaturated polyester resin C was with 30% styrene and 0.01% hydroquinone mixed, an unsaturated polyesterhan: solution C-I was obtained on which the Percentages are based. 163 parts of the polyvinyl chloride plastisol were used to make Sample No. 8 (c) and 2.6 parts of benzoyl peroxide are added to 100 parts of the solution C-1 and to the one thus obtained

52 parts of magnesium oxide were added to the mixture for 3 seconds. To prepare control sample No. 9, 1 part of benzoyl peroxide and 2 parts of magnesium oxide were dispersed in 100 parts of the unsaturated polyester solution CI.
Samples No. S uno 9 / eigteii show a gradual increase in viscosity even at room temperature. When the viscosity increase was supported by heating to 4OX for one hour, sample no. 8 and sample no. 9 gave a semi-gel-like solid.
Table 2 shows the hardening properties of samples No. 8 and 9, as well as the increase in viscosity of these samples and the physical properties of products made therefrom by casting.
In spite of the low maximum temperature of the exothermic reaction, sample No. 8 gave a cast product of high hardness, high tensile strength and high flexural strength and with a high modulus of elasticity and a high dimensional stability limit. The product made from Sample No. 8 by casting thus had excellent mechanical strength, low volume shrinkage and good self-extinguishing effect.

Sample # 8 Sample No. 9 Remarks (according to the invention) (Control sample) Curing properties Time to start of gel formation 8:02 7:47 JlS K-6901 (min: see) Minimum curing time (min: see) 10:55 10:50 JlS K-6901 Maximum temperature at the exothermic 128 195 ] 1S K-6901 Reaction (° C)

• I 23 continuation 21 55 655 24 Sample No. 9 Remarks I 5 (Control sample) Condition of increased viscosity Sample # 8 small amount Adhesiveness (according to the invention) semi-gelatinous almost equal Hardness of the product with increased viscosity Physical properties of the cast small amount Product semi-gelatinous 9.1 Volume shrinkage (%) 120 ASTM D-785 Hardness, (Rockwell R) 3.87 JIS K-6911 Tensile strength (kp / mm ² ) 3.0 2 JIS K-6911 Strain (%) 127 12.4 JlS K-6911 Flexural strength (kp / mm ² ) 4.68 350 JlS K-6911 Young's modulus (kp / mm ² ) 2 2.0 JlS K-6911 Impact strength (Izod method) 12.4 (kp cm / mm ² ) 415 95 ASTM D-648 Dimensional stability limit (° C) 4.2 (18.5 kg / cm ² ) easily flammable Flame resistance 118 Example For D i e 1 4 self-extinguishing

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomer, Polymerization initiator and thickener.

From the samples No. 8 and 9 prepared in Example 3, cured products were made and

(1) the boiling water immersion test,

(2) the immersion test in 40 percent sulfuric acid at 70 ⁰ C,

(3) the immersion test in 15 percent caustic soda at 70 ⁰ C and

(4) subjected to the radiation test with the xenon weatherometer. After these exams the remaining flexural strength was measured in% of the original flexural strength. The results are given in Table 3 and show that the product of the invention Sample No. 8 had better chemical and weather resistance than the product from of control sample No. 9.

Table 3 __

Remaining flexural strength in% of the original flexural strength

Sample No. 8 Sample No. 9 (according to the (control invention) sample)

Composition of vinyl chloride polymer. reactive plasticizer, unsaturated polyester resin. Vinyl monomers, Polymerization initiator and thickener

In the manner indicated in the above examples, the pasty samples Nos. 10 and 11 were obtained with the compositions given in Table 4.

Table 4

Composition (parts) Sample # 11 - Sample # 10 (Control (according to the sample) Invention) 100 Vinyl chloride polymer 100 for paste 60 Ethylene glycol dimeth 60 acrylate 300 Unsaturated polyester 300 resin solution C-I Stabilizer for vinyl 3 chloride polymer 3 (Zn / Cd / Ba type) 4.6 tert-butyl perbenzoate 4.6 Calcium hydroxide 23

52

After soaking in boiling for 500 hours water

After 30 days of immersion in 40 percent Sulfuric acid at 70 ° C After 30 days of immersion in 15 percent Caustic soda at 70 ° C After 100 hours Xenon radiation (The test item was 25 80 χ 3 mm in size.)

71

32

85

The viscosity of the paste-like sample No. 10 slowly increased even at room temperature. When the increase in viscosity was assisted by heating at 50 ° C. for one hour, the paste formed a semi-gel-like solid. When the paste-like sample No. 11 containing no thickener was left to stand for a long time, precipitation of the vinyl chloride polymer was observed the thickener contained cast made products. Table 5 shows the scatter of the mechanical properties.

609 636''18O

According to the procedure according to jlSK-6911, 5.4 the deformability of Samples Nos. 10 and 11 was determined. A large shape was used for this, the Dimensions of 30 30 χ 5 cm and a mold wall thickness of 3 mm. That from sample no.10 Product made with the help of the mold had an excellent surface quality, while the one from

Table 5

of Sample No. 11 in the mold-made product had a less smooth surface, and shrinkage, deformation, and deep, narrow holes were found in this product. Processing in the mold took place during a curing time of 5 min at 140 ^° C. under a pressure of 50 kp / cm ² .

Condition in the container

Sample # 10
(according to the invention) semi-solid without settling of the vinyl chloride polymer

Sample # 11

(Control sample)

liquid with settling

of vinyl chloride polymer

Remarks

Heated to 50 "C for 1 hour

Cast product

Flexural strength (kp / mm ² )
[Scattering*)]

Young's modulus (kp / mm ² )
[Scattering*)]

Flame resistance

12.0 (1.1)

410 (9)

self-extinguishing 12.1
(6.2)

415
(21)

self-extinguishing

Moldability _moderate good ß _ig JIS K-6911 54

·) The spread is equal to the difference between the highest and lowest who. with five test items.

Example 6

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomers. Polymerization initiator and thickener

In the manner shown in Example 1, Sample No. 12 having that shown in Table 6 was obtained Composition made. After standing at room temperature for 24 hours, the mass was semi-gel-like. A product made by thermosetting the mass in a mold was also excellent Properties like the product made from Sample No. 8 in Example 3 in a mold.

Table 6

Together settlement (Parts) Sample No. 12 (according to the Invention) Vinyl chloride polymer for paste 100 Trimethylol trimethacrylate 100 Unsaturated polyester resin solution B-I 400 Stabilizer for vinyl chloride polymer 3 Zinc acetate 30th tert-butyl perbenzoate 6th

1160 and the average degree of condensation 13 Then were used to produce an unsaturated

Polyesierharzlösung 40 parts of the unsaturated poly Ester resin D dissolved in 60 parts of diallyl phthalate and 0.01 part of hydroquinone was added to the solution.

With the help of the unsaturated polyester resin solution D-I was specified in the above examples

We ₁ Se prepared a sample No. 13, the composition of which is given in Table 7.

The mass obtained consisted of a semi-gel-like Solid with poor tackiness. If you hardened this mass in a mold at 140 ° C for 30 minutes.

elucidate a product in terms of volume shrinkage and mechanical and chemical t properties was good as the product obtained in Example 3 from sample No. 8 in a mold.

Table 7

Composition (parts)

Sample No. 13 (according to the invention)

Example 7

Composition of vinyl chloride polymer, reactive Plasticizer, unsaturated polyester resin, polymerization initiator and thickener

In the reaction vessel also used in Example 1, 0.4 mol phthalic anhydride, 0.6 mol Maleic anhydride, 0.7 mol of neopentyl glycol and 0.4 mol of ethylene glycol reacted. The thereby formed Unsaturated polyester resin D had an acid value of 20, the number average molecular weight Vinyl chloride polymer for paste trimethylpropane trimethacrylate Stabilizer (liquid organic "Zn / Cd / Ba complex) tert-butyl perbenzoate Unsaturated polyester resin solution D-I zinc acetate

100

60

100 13

Example! 8th

Composition of vinyl chloride polymer, reactive Plasticizer unsaturated polyester resin, vinyl monomer, polymerization initiator and thickener

100 parts of the sample No. 1 prepared according to Example 5 were mixed with 20 parts of titanium dioxide and 120 parts

Calcium carbonate combined and good in a kneader mixed. In a short time 80 parts of stacked glass fiber 8 mm in length and 1 part of benzoyl peroxide were added to the mixture and 2 parts calcium hydroxide added, whereby a molding compound in the form of a bulk material (sample no. 14) was obtained. Immediately after its production, this mass was somewhat tacky. After standing for 24 hours no more adhesiveness could be determined and the mass could be manipulated very easily.

The mass was compression molded in a hot compression molding machine for 3 minutes at 140 ^° C. and under a pressure of 50 kgf / cm ^2. During compression molding, the mass had excellent flowability. The pressed molded body had a smooth surface, a Rockwell M hardness of 98, a flexural strength of 8 kp / mm- 'and a FJasii / iiätsmudul of 1020 kp / mm ·'.

Example 9

Composition of vinyl chloride polymer. responsive Plasticizer, unsaturated polyester resin. Vinyl monomer. Polymerization initiator and thickener

! Line molding compound was made from JO I rush a vinyl chloride polymer for paste. 2 parts of one Stabilizer (liquid organic Cd / Ba / Zn complex). 20 parts of diethylene glycol dimethacrylate and 48 parts of the unsaturated polyester resin solution A-I. For the preparation of the samples No. 15, 16 and 17 were of the molding compound 1 part, 2 parts and 3 parts magnesium oxide / ugcsctzi .. These mixtures were in one Fast mixer mixed thoroughly. Then, with the help of a Brookfield viscometer, the Change in viscosity noted.

ίο For comparison, the change in Viscosity of control masses (samples nos. 18, 19 and 20), for their preparation of the unsaturated polyester resin solution A-I! Part, 2 parts and 3 parts, respectively Magnesium oxide were added. The results are

ι s also given in Table 8.

In the compositions according to the invention, the viscosity decreased over a period of 5 to 48 hours the addition of magnesium oxide quickly and then only a little. Furthermore, these masses lost during

: o a period of 24 to 48 hours after the addition of magnesium oxide its ability to cling.

In the case of the compositions made from the unsaturated polyester resin used for comparison, the viscosity increased on the other hand much slower. Even 48 to 100 hours

is after the addition of the magnesium oxide they were Masses still sticky.

Table 8

Samples According to the Invention No.16 No. 17 Control samples No. 19 No. 20 No. 15 No. 18 Composition (parts) 30th 30th - - Vinyl chloride porymerisate for paste 30th 2 2 - - - Stabilizer (liquid organic 2 - Cd / Ba / Zn complex) 20th 20th - - Diethylene glycol dimethacrylate 20th 48 48 - 100 100 Unsaturated polyester solution A-I 48 2 3 100 2 3 Magnesium oxide 1 1 Viscosity (poise) 20th 20th 5 5 Immediately after production 20th 100 1000 5 18th 20th 5 hours after production 50 500 3400 16 35 50 10 hours after production 160 2100 10,000 22nd 55 300 24 hours after production 600 4400 13000 30th 10Ö 5000 48 hours after manufacture 2600 5400 18000 60 4500 14,000 100 h after production 3200 1500

Example 10

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomers. Polymerization initiator and thickener

In the reaction vessel also used in Example 1, 1 mole of isophthalic acid was added. 1 mol of maleic anhydride, 1.08 mol of propylene glycol, 0.1 mol of dipropylene glycol and 037 mol of neopentyl glycol reacted. The unsaturated polyester resin thus formed E had the acid number of 29, the numerically average molecular weight of 1460 and the average degree of condensation of 15 by the addition of 30% styrene and ss 00:01% hydroquinone to the unsaturated polyester resin to give the unsaturated polyester resin solution EI to which the percentages are by .

From 30 parts of a vinyl chloride polymer for paste, 2 parts of a stabilizer (liquid organic Cd / Ba / Zn complex), 20 parts of diethylene glycol dimethacrylate and 48 parts of the unsaturated polyester resin solution E-I a molding compound was produced.

By mixing 100 parts of the molding compound with 30 parts of calcium carbonate, 5 parts of titanium dioxide, 10 parts

6s Styrc.lmonomerem and 1 part benzoyl peroxide and a mixer and the subsequent addition of 2 parts of magnesium oxide became a liquid mass educated

Immediately after the production of the liquid mass, it was turned into it using an itakel coating machine a thin coating was formed on a polyethylene film sprinkled evenly on the coated film. Another film coated with the liquid mass was placed with the coated surface on the film covered with the pieces of fiberglass, whereupon the arrangement was degassed by means of a roller. In this way, a molding compound in the form of a ro was obtained Foil (sample no. 21) in which the mass wetted the pieces of fiberglass strand well.

24 hours after the molding compound had been produced in the form of a film, it was not tacky even after the polyethylene film had been peeled off. The mass was very flexible. It contained 35% glass fibers. This molding compound in the form of a film was cut into sheets of 25 × 25 cm. Eight of these sheets were superposed and 3 minutes under a pressure of 150kp / cm ² at 140 ⁰ C molded The Formpreßprodukt thus obtained had a smooth surface, a Rockwell M hardness of 102, a tensile strength of 14.2 kgf / mm ^2, a flexural strength of 24.1 kp / mm ² and a modulus of elasticity of 1150 kp / mm ² .

Example 11

Mass of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomer, non-reactive plasticizer, polymerization initiator, thickener and blistering material

In the manner indicated in Example 1, a mixture of the polyvinyl chloride plastisol (a) and the unsaturated polyester resin solution A-I prepared. Phenolic resin microballoons with occluded Nitrogen gas added, as well as magnesium oxide and benzene peroxide (sample No. 22).

For comparison, compositions were prepared in the manner indicated above which did not contain magnesium oxide (Sample No. 23) or no polyvinyl chloride plastisol (a) (Sample Nos. 24 and 25). The composition Table 9 shows these samples.

A sheet 20 cm long, 30 cm wide and 5 mm thick was produced from each sample by casting and ^{cured in an oven at 140 °} C. for 20 minutes

After standing for 24 hours, sample no. 22 made from the composition of the invention was semi-gelatinous. Self if left to stand for a very long time, the microballoons did not separate, but remained the mass homogeneous. The product made of Sample No. 22 by casting became uniform when heated foamed. The molded body produced therefrom was brown in color and had an expansion ratio of about 2.5. It had a relatively uniform surface layer on its periphery in contact with the mold about 1.5 mm thick. At its core, the fenn body had a cellular structure evenly distributed, pile-shaped, continuous cells with a diameter of 0.5 to 1.0 mm.

Sample No. 23 was liquid. When stored, the microballoons separated easily. By the Pouring, curing and foaming this sample gave a product similar to that of sample no. 22 produced product, but in terms of expansion ratio and evenness was inferior to the cells. When samples 24 and 25 were heated and cured, the Difference from samples nos. 22 and 23, no even foaming, but sometimes very strong foaming achieved The products made from samples Nos. 24 and 25 showed very strong foaming Shrinkage and, in places, cracks and discrepancies. · Ο that they had no practical value.

Table 9

Composition (parts)
Invention control samples
appropriate sample
No. 22 No. 23 No. 24

No. 25

Unsaturated polyester resin solution A-I

Vinyl chloride polymer for paste

Di (2-ethylhexyl) phthalate

Ethylene glycol dimethacrylate

Stabilizer (liquid organic Cd / oa / Zn complex) Phenolic resin microbdlones

Benzoyl peroxide

Magnesium oxide

200 200 100 4th 100 100 - 1 30th 30th - 2 30th 30th - 3 3 - 10 10 3 3 7.2

100

Example 12

Made from vinyl chloride polymer. responsive Plasticizers, unsaturated polyester, vinyl monomers. Polymerization initiator. Thickeners and

Blistering material

In the Rcaktionsgc also used in Example 1 1 mole of isophthalic acid was used as a barrel. 1 mole of maleic anhydride. 1 mole of neopentyl glycol and 1 mole of diethylene glycol! implemented. An unsaturated polyester resin was obtained F has the acid value 25, the number average molecular weight 2460 and the average degree of condensation 23. 30% styrene and 0.01% were added to the unsaturated polyester resin 0.01% hydroquinone added, whereby the unsaturated polymer resin solution F-I was formed, onto which the Pro7cntiingabcn are related.

By mixing 60 parts of the unsaturated polyester resin solution F-I, 20 parts of a vinyl chloride polymer for paste, 12 parts of ethylene glycol dimethaerylate, 0.6 part of a stabilizer (Cd / Ba / Zn type) 09 part of tert-butyl perbenzoate. 10 parts titanium dioxide, 40 Share sodium borosilicate microballoons with occluded air and 1 part zinc stearate in a kneader a molding compound is produced, which then quickly contains 40 parts of 8 mm long staple silk and 1 part of tert-butyl perbenzoate and 1 part of magnesium oxide was added. In this way, a molding material in the form of a Bulk material (sample no. 26) formed.

Immediately after its production, this mass was somewhat tacky. 24 hours after its creation was the However, the mass was not at all adhesive and could be manipulated very easily.

In a Warmformpreßmaschine the mass was 3 min under a pressure of 50 kgf / cm * compression molded at a temperature of 140 ⁰ C. During the compression molding process, the mass flowed well. The molded body produced therefrom was light and had a smooth surface.

Example 13

Mass of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, polymerization initiator, Thickener and blistering material

From 30 parts of a vinyl chloride polymer for paste, 2 parts of a stabilizer (liquid organic Cd / Ba / Zn complex). 20 parts of trimethylolpropane trimethacrylate and 48 parts of the unsaturated polyester resin D-I, a dispersion was prepared.

In a mixer, 100 parts of this dispersion were mixed with 5 parts of titanium dioxide, 20 parts of glass microballoons, 10 parts of styrene monomer and 1 part of tert-butyl perbenzoate mixed. By adding 2 parts of magnesium oxide to the mixture, it became liquid Formed mass, from the in the manner specified in Example 10, a molding compound in the form of a Film (sample No. 27) was prepared.

This molding compound in the form of a film and the product made therefrom in a mold had similar ones Properties like the molding compound or the molded body according to Example 10. The from sample no. 27 in however, a product made in a mold had a lower density than that made in a mold Product according to example 10.

Example 14

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomers. Polymerization initiator, thickener

and blistering material

In the reaction vessel also used in Example 1 1 mole of isophthalic acid, 1 mole of maleic anhydride, 1 mole of neopentyl glycol and 1 mole of 1,6-hexanediol implemented. The resulting unsaturated polyester resin G had an acid value of 28, that is numerically average molecular weight 2000 and the average degree of condensation 18. Then became an unsaturated one by adding 30% styrene and 0.01% hydroquinone to the unsaturated polyester resin Polyester resin solution G-I formed, to which both percentages are based.

The composition given below for Sample No. 28 was mixed thoroughly with agitation and then degassed under reduced pressure. A 4 mm thick coating was applied to a sheet of plywood from the mass. An identical plate was arranged in a mirror-inverted manner above this in such a way that there was a gap of 4 mm between the coated surfaces. ^{The arrangement was heated to 150 °} C. for 10 minutes in a hot press. The coating composition was skimmed off with a foaming ratio of 2 and a laminated body was obtained which had an 8 mm thick foam layer.

Composition of sample No. 28

Parts
100

60

200

7th
10

Vinyl chloride polymer for paste (average Degree of polymerization 1700)

Reactive plasticizer (tri

methylol propane trimethacrylate

Unsaturated polyester resin solution Eq
. ₀ stabilizer (same as in example 1)

Blistering material (phenolic resin

Microballoons)

tert-butyl perbenzoate 5

Soot 5

Magnesium oxide 7.8

The properties of the laminate sheet obtained in this way were determined and are in the Table 10 given. For comparison, plywood laminated panels were also tested using of ordinary polyvinyl chloride films (sample No. 29) and ordinary polyester films, respectively (Sample No. 30) were obtained. The results are also given in Table 10.

Table 10

Sample No. 28
(according to the
Invention)

Control sample:
No. 29

No. 30

Surface hardness (with Barcol hardness tester)

Surface abrasion coefficient (Taber abrasion device)

Thermal conductivity (10 ~ <cal / sec / cm * / ⁰ C)

Soundproofing

Flammability (if the middle part of the surface of the laminate board comes into contact with a flame)

80 34 90 1.5 10.5 3.5 0.9 5.0 moderate small amount get

hardly flammable, hardly flammable, light
self-extinguishing self-extinguishing combustible

Example 15 Composition of vinyl chloride polymer, reactive Plasticizer, unsaturated polyester resin, vinyl mo-

nomeric, reactive plasticizer, Verdik agent and polymerization initiator

A mixture was prepared with the following composition:

Components Parts Vinyl chloride polymer (avg 100 licher degree of polymerisation 1700) Reactive plasticizer 30th (Diallyl phthalate) Unsaturated polyester resin solution A-I 50 Dioeyl phthalate (DOP) 30th Benzoyl peroxide
Stabilizer for vinyl chloride dolly 2
5

Example 16

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, reactive

incompetent plasticizer. Polymerization initiator and thickener

To prepare an unsaturated polyester resin solution A2, 0.01 part of hydroquinone was introduced into a solution of 60 parts of the unsaturated polyester resin A prepared according to Example I in 40 parts of ethylene glycol dimethacrylate. 200 parts of the unsaturated polyester resin solution A-2 were mixed with 163 parts of the polyvinyl chloride plastisol (a) produced in Example I. 2 parts of magnesium oxide and 3.6 parts of benzoyl peroxide mixed. The mixture was mixed thoroughly in a mixer and ^{heated to 50 °} C. for 1 hour. This turned the flowable mixture into a semi-gelatinous solid with poor adhesiveness. A product was produced from this solid in the manner indicated in Example 1 by casting, the properties of which were determined. The product had a volume shrinkage of 4.1% and a Rockwell R hardness of 129. It had excellent appearance and high impact resistance, like the product made by casting from Sample No. 1 of Example 1, and was self-extinguishing.

'5

40

45

55

60

Example 17

(Zn / Cd / Ba type)

Magnesium oxide 4.6

The mixture was stirred thoroughly, poured onto a flat plate and then heated ^{to 150 ° C. for 5 min.} A sheet 3 mm thick was obtained in this way. A 3 mm thick sheet of polyvinyl chloride was placed on top of this. The arrangement was heated to 160 to 170 ^° C. for 3 minutes in a hot press. Here, the vinyl chloride polymer and contained in the bottom sheet, the vinyl chloride polymer contained in the vinyl chloride sheet was melted and diffused this Vinylchloridpolymerisatanteile each other, so that they were welded together. If the welding area was relatively small, the welding was done with the help of high frequency or ultrasonic energy.

Mass of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, non-reactive Plasticizer, polymerisation initiator, thickener and blistering material

In the manner indicated in Example 16, a mixture of 163 parts of the polyvinyl chloride plastisol (a) and 200 parts of the unsaturated polyester resin solution A-2. The mixture became 10 parts »Shirasuglastt microballoons and then 3 parts benzoyl peroxide and 7.2 parts of magnesium oxide mixed in.

Immediately after its manufacture, the mixture was flowable and the microballoons tended to float into the upper part of the mixture. To However, when left standing at room temperature for 24 hours, the mixture had a higher viscosity and was found to be himself in a semi-vulture state. After the semi-gel-like mixture stir evenly had been mixed, the microballoons no longer floated in the upper part. but stayed that way Mixture homogeneous. The mixture was then poured under the conditions given in Example 11, heated and cured. A foam molded body was obtained, which on its from the mold touched perimeter had a dense surface layer and had regular, pile-like cells in its core. The foam body had an expansion ratio of about 1.8 and different from those in the example 11, control samples Nos. 23, 24 and 25 were prepared in terms of cell structure and reproducibility the foaming ratio has the same good properties as that in Example 11 of Sample No. 22 manufactured foam product.

Example 18

Composition of vinyl chloride polymer, reactive plasticizer, unsaturated polyester resin, vinyl monomers. non-reactive plasticizer, polymerization initiator, thickener and blistering material

In the manner given in Example 11 for Sample Nos. 22, 23, 24 and 25, Sample No. 31 of the invention was prepared from the composition of the invention and Control Sample No. 32, 33 and 34 were prepared, but instead of the phenolic resin microballoons zeolite saturated with carbon dioxide gas was used. The masses obtained in this way and the cured Schaunisstoffprodukte produced therefrom had similar properties to the masses or molded articles produced in Example 11. The best results were achieved with sample no. 31 made from the composition according to the invention ¹ . On the other hand, a very poor foam was obtained from the zeolite-containing compositions which contained only the unsaturated polyester resin as a resin component (samples Nos. 33 and 34 corresponding to samples 24 and 25 in Example II). In the foam product of Sample No. 31, the expansion ratio was about 2, the surface layer was 1 to 1.5 mm thick, and the pile-like cells in the core were 0.2 to 1.5 mm in diameter. The cell distribution in this foam product was somewhat uneven.

For this purpose 2 sheets of drawings

Claims (1)

" ..,. Claim: Thermosetting molding compound, consisting of
** A. 5 to 60 percent by weight vinyl chloride polymer ■ "sat, B. 5 to 60 percent by weight unsaturated polyester resin which has an average degree of condensation of at least 4 and a number average molecular weight of at least 1000,
C at most 60 percent by weight more reactive Plasticizers and
D. if necessary additionally a) a non-reactive plasticizer, ι s b) a vinyl monomer, c) 0.2 to 3 percent by weight polymerization initiator, d) 1 to 50 weight percent of a bubbling agent and e) a filler, characterized in that it is 0.1 to 10 Weight percent beryllium oxide, magnesium oxide, strontium oxide, barium oxide, beryllium hydroxide, magnesium hydroxide, Contains calcium hydroxide, strontium hydroxide or barium hydroxide.