GB1592346A

GB1592346A - Moulding compositions comprising glass particles and a polymeric binder

Info

Publication number: GB1592346A
Application number: GB2136776A
Authority: GB
Original assignee: KROYER KKK
Current assignee: KROYER KKK
Priority date: 1976-05-24
Filing date: 1976-05-24
Publication date: 1981-07-08
Also published as: BE854997A

Description

(54) MOULDING COMPOSITIONS COMPRISING GLASS PARTICLES AND A POLYMERIC BINDER (71) I, KARL KRISTIAN KOBS KRYER, of Danish nationality, of Banegaadspladsen 4, DK-8100 Aarhus C, Denmark, do hereby declare the invention for which I pray that a patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to moulding compositions which are useful in the production of moulded articles having excellent mechanical properties, in particular high mechanical strength.

In accordance with the present invention there is provided a moulding composition comprising, in admixture, particles of a coarse aggregate and a binder therefor, wherein the coarse aggregate comprises particles of ground glass having a particle size in the range 250 to 5000 Fm and obtained by grinding a crystallizable or crystallized glass of a type having a mass of microbubbles dispersed throughout the glass, and wherein the binder comprises an intimate blend of an organic thermoplastic or thermosetting resin and a finely-divided filler, said filler likewise comprising particles of ground glass obtained by grinding a crystallizable or crystallized glass of a type having a mass of microbubbles dispersed therein, but having a particle size less than 250 clam.

Also included are moulded articles formed from the above compositions by moulding under heat and pressure.

The preferred aggregate and finely divided filler is crystallized glass made in a rotary kiln as described for example in U.K. Patent No. 992,783, and ground to a suitable particle size, for example by using a ball mill. A product of this kind is known as 'Synopal' glass. 'Synopal' is a Registered Trade Mark.

'Synopal' is characterised by a mass of microbubbles dispersed throughout the glass, and when such particles are ground, the surfaces of the ground particles are rough and have numerous cavities resulting from fracture through the bubbles. Due to this surface structure the ground particles adhere well to organic resins and to each other in interlocking relationship.

The particle size of the finely divided filler can be varied to suit the use but, in general, will be less than 250 calm and preferably not exceeding 150 m. Particles having an ideal fineness characteristic, i.e. of a particle size distribution to permit dense packing of the particles, are preferred.

As the resin component of the binder can be used any organic resin. Examples of suitable resins are thermosetting resins or cold curing resins, such as epoxy resins, melamine resins, urea formaldehyde resins, unsaturated polyesters, urethane resins and phenol formaldehyde resins, or thermoplastic resins, such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polyacrylates, polystyrene, polyamides and polycarbonates.

The ratio between filler particles and the organic resin in the binder can be varied within wide limits. The proportion of resin should be kept as small as possible without reducing the desired mechanical properties. An amount of 5-20 % resin, e.g. 10% resin, is suitable for most purposes. More resin can be used, for example 20-30% resin or 30-50% resin, if desired.

Also, smaller amounts of resin can be used, for example 2-5% resin. Normally, this will reduce the mechanical strength and other properties of the final product. Generally preferred are amounts in the range 5-10%by weight.

The mixing of the filler and the resin is carried out in such a way that the resin, usually in powder form, is ground into the interstices and the surface irregularities of the filler particles.

Preferably the filler and resin are mixed by dry grinding, preferably in a ball mill. The mixing process may sometimes be facilitated by adding a solvent, or the resin may be introduced as a solution of the organic resin in a suitable solvent or as a suspension or emulsion in water. As the solvent can be used any conventional solvent for resins. Normally, the solvent evaporates during the mixing procedure. If desired a minor amount of a fibrous filler may be incorporated into the binder during the grinding operation.

If desired, it is possible to add also minor amounts of various additives or adjuvants to achieve desired effects or as fillers. Hence, silicon oxides or silicates may be added. For example, Aerosil (Registered Trade Mark) added to the binder in amounts of from 0.01 to 1 % by weight will result in increased fluidity, improved density and uniformity of the finished product.

Other additives suitable in small or moderate amounts are small glass spheres, short mineral fibres, for example of glass or rockwool, and pigments. Also, the products may be reinforced by metal threads or grating, glass fibre mats or woven cloth, cellulose fibres, paper or the like. Pigmentation will produce various decorative effects. By mixing fractions of different colours it is also possible to obtain various marbled patterns.

The amount and particle size of the coarse aggregate particles to be mixed with the binder depend on the end use of the articles and the technology available for the forming process.

For most purposes particle sizes from 250 to 1000 m are suitable. Even coarser particles can be used, however, for example 1-5 mm, especially when articles of large dimensions are to be produced. The ratio of coarse particles to binder depends on the type of particles, the use and the desired properties of the product and may vary within wide limits. For example, 1 to 5 parts by weight of coarse particle to 1 part by weight of binder is generally suitable.

The compositions of this invention may be compressed or formed in any other desired manner to produce strong articles having extremely low resin content, based on the total mix.

As the organic resin is by far the most expensive component of the mixture, very cheap products having satisfactory or excellent characteristics can be obtained.

'The compositions of the invention can be fonnulated to obtain a large variety of properties of the end products. Thus, the formulation can be modified in order to obtain products having high mechanical strength, increased weather resistance, high porosity or non-porosity, and different colour effects.

The accompanying drawing shows a section through a moulded composition according to the invention and composed of coarse particles of crystallized glass having interior bubbles 3 and bubbles 4 penetrating the surface of the coarse particles 1. The coarse particles 1 are held together with a binder2 consisting of fine crystallized glass particles 5 embedded in resin. The matrix also fills the open surface bubbles or cavities 4 providing anchoring between the coarse particles.

The invention will be further explained below by way of examples. All percentages are on a weight basis.

EXAMPLE 1 This example describes two'binders which may be used in the compositions of this invention.

The following ingedients are mixed: PhenolicResin 12-16% Synopal 0- 140 80 - 85 % Metal Oxides 0- 4% or Epoxy Resin 15 - 20 % Sand 300,am 20 - 25 % 'SynopalO- 140 CLm 55% Metal Oxides 5% EXAMPLE 2 This example describes compositions according to the invention which may be used for tiles. It is possible to produce ordinary wall tiles to be used for decoration only, e.g. above a dining table standing against a wall. The can be used in the same way as ceramic tiles but they are much cheaper and easier to mount on the wall, too. No qualified craftsmen are needed.

Phenolic Resin 3- 7% Synopal 0- 140 m 35 - 40% Synopal 200 - 600 m 50 - 58% Metal Oxides 0- 4% or Epoxy Resin 5 - 10% Nylon 5 - 10% Synopal 0- 140 m 25 - 30% Synopal 200 - 600 m 45 - 50 % Metal Oxides 0- 5% EXAMPLE 3 This example illustrates another binder composition which may be used in the compositions of this invention.

Phenolic Resin 6 - 10% Cement Powder 0 - 150 m 18 - 22% Synopal 0 - 140 m 68 - 72% Organic Pigments 0- 2% EXAMPLE 4 This example illustrates compositions according to this invention and containing both fine and coarse Synopal particles.

Phenolic Resin 3.5 - 4.0% Synopal 0 - 140 m 33 - 35% Synopal 0 - 500 m 18 - 22% Synopal 500 - 1500 m 18 - 22% Synopal 1500 - 2000 m 18 - 22% Metal Oxides 0 - 4% or Polyester Powder 5- 8% Synopal 0 - 140 m 30 - 36% Synopal 0 - 500 m 16 - 18% Sand 500 to 1500 m 16 - 18% Granite Pebbles 2000-4000 m 22 - 24% Metal Oxides 0- 4% EXAMPLE 5 Other compositions useful as binders in accordance with this invention are as follows: Epoxy Resin 20% Copper Powder 5% Synopal 0- 140 m 75% (Silane Coated) Epoxy Resin 18 % Synopal 0- 140 m 74% (Silane Coated) Metal Oxides 4% Melamine Resin 4% EXAMPLE 6 Yet another binder composition suitable for use in this invention is as follows:: Phenolic Resin 5- 8% Synopal 0 - 140,um 88 - 92 % Metal Oxides 2- 4% EXAMPLE 7 For critical applications where water is present, either as rain or at sea, a water repellent effect can be achieved using a binder of the following composition: Epoxy Resin 18% Silicone Resin 2% Copper Powder 5% Synopal 0- 140 m 75% (Silane Coated) EXAMPLE 8 Other elements than metal sheets, - wooden chipboard, insulating board, abestos/cement sheets etc. can be coated, too. In some cases the element has been manufactured in advance, and there the recipe of Example 6 could be used. However, it is often desirable to apply a heavy layer of the matrix, partly for strength reasons, partly for fire-proofness reasons.In that case it is advisable to use the following recipe because the matrix is richer than the others with respect to resin content, and consequently it will adhere to the surface of the element simultaneously with the moulding. The composition containing large particles is placed on top of the element (or in the cavity with the element on top), and the upper part of the compression tool moves down, moulding and curing the composition and pressing out the resin of the binder into the surface of the element.

For Chipboard: Phenolic Resin 10 - 14% Synopal 0 - 140 m 30 - 40% Synopal 2000 - 4000 m 50 - 60% Organic Pigments 0- 2% Titanium Dioxide 3% EXAMPLE 9 Exceptionally high mechanical strength can be achieved through the addition of short glass fibres which are admixed with the composition in the last period of ball milling. These glass fibres must be very thin to ensure that the reinforcing effect is obtained. Such high mechanical strength is desirable in the case of roof tiles or outer wall elements without further support from existing elements. The addition of a silicone resin makes the tile water-repellent and improves its impact strength properties. The addition of a VU-stabilizer improves weathering properties.

Phenolic Resin 4% Silicone Resin 1 % UV - Stabilizer 0.2% Synopal 0- 140 m 30% Synopal 600 - 840 m 30% Sand 800 - 1200 m 30% Glass Fibres 2% Metal Oxides 2.8 % EXAMPLE 10 For the manufacture of serving trays, dining tables and heat protection boards for domestic use, the following composition may be moulded in contact with a melamine impregnated paper decoration: Dry Formed Paper Mixture (cellulose fibre 25%, Synopal 0-140 m 25% and melamine 50%) 5 % Phenolic Resin 5 % Synopal 0 - 140 m 40 % Synopal 200 - 600 m 48 % Organic Pigments 2 % EXAMPLE 11 The following samples were produced having a low content of resin binder and containing different amounts of coarse mineral particles:: Sample No. 1 Synopal 0 - 140 m 34.2 % 0 - 500 m 20.0 % 500 - 1500 m 20.0 % 1500 - 2000 m 20.0 % 94.2 % Phenolic Resin 3.8 % Metal Oxides 2.0 % This recipe is useful only for heavy products.

Sample No. 2 Synopal 0 - 140 m 36 % 0 - 500 m 16 % 500 - 1500 m 20 % 1500 - 2000 m 22 % 94% Phenolic Resin 4% Metal Oxides 2% This recipe is useful only for heavy products.

Sample No.3 Synopal 0 - 140 m 36 % 600 - 840 m 60 % 96% Phenolic Resin 4% A specimen cast from this material had good strength.

Sample No.4 Synopal 0 - 140 m 36 % 200 - 600 m 60 % 96% Phenolic Resin 4% The sample had high strength, and the recipe is useful for both thin and heavy products.

EXAMPLE 12 A number of samples were produced having the following compositions: Sample 1 Synopal O- 140,um 74 % 500- 1500,um 20 % 94% Phenolic Resin 6% Synopal 0- 140,um '35% 200-600m 59 59% 94% Phenolic Resin 4% Metal Oxides 2% EXAMPLE 13 A mixture of 90 parts by weight of Synopal and 10 parts by weight of phenolic resin is ground in a ball mill to a particle size of from 0 to 150 ,um. This binder is mixed with equal parts by weight of Synopal with a particle size of from 250 to 1500 cam. The mixture is used as a moulding composition for manufacturing roofing sheets. The sheets are pressed in a die or mould, heated to 210 C for 20 seconds. For final curing the sheets are heated with direct flames in an oven for 2 minutes. This treatment will complete the curing of the resin and burn the developed volatile gases, especially formaldehyde.

WHAT WE CLAIM IS: 1. A moulding composition comprising, in admixture, particles of a coarse aggregate and a binder therefor, wherein the coarse aggregate comprises particles of ground glass having a particle size in the range 250 to 5000m and obtained by grinding a crystallizable or crystallized glass of a type having a mass of microbubbles dispersed throughout the glass, and wherein the binder comprises an intimate blend of an organic thermoplastic or thermosetting resin and a finely-divided filler, said filler likewise comprising particles of ground glass obtained by grinding a crystallizable or crystallized glass of a type having a mass of microbubbles dispersed therein, but having a particle size less than 250 m.

2. A composition according to claim 1, wherein the particle size of the coarse aggregate is in the range 250 to 1000 ism.

3. A composition according to claim 1 or 2, wherein the finely divided filler particles have a maximum particle size not exceeding 150,um.

4. A composition according to any one of claims 1 to 3, wherein the weight ratio of said aggregate to said binder is from 1:1 to 5:1.

5. A composition according to any one of claims 1 to 4, wherein the organic resin constitutes from 5 to 10% by weight of the binder.

6. A composition according to any one of the preceding claims, wherein the organic resin is a thermosetting resin.

7. A composition according to claim 6, wherein the thermosetting resin is a phenol formaldehyde resin.

8. A composition according to claim 1, substantially as hereinbefore described in any one of the Examples.

9. A composition according to any one of the preceding claims, wherein the binder additionally contains a minor amount of a fibrous filler.

10. A moulded article comprising a composition according to any one of the preceding claims which has been compression moulded under heat and pressure.

11. A method of forming a composition according to any one of claims 1 to 9 which comprises grinding the crystallizable glass particles in the presence of the organic resin to form said binder, and subsequently adding to the binder the coarse aggregate particles.

12. A method according to claim 11, wherein the crystallizable glass particles are dry ground with said resin in powder form.

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Claims

**WARNING** start of CLMS field may overlap end of DESC **.

EXAMPLE 12 A number of samples were produced having the following compositions: Sample 1 Synopal O- 140,um 74 %

500- 1500,um 20 % 94% Phenolic Resin 6% Synopal 0- 140,um '35% 200-600m 59 59% 94% Phenolic Resin 4% Metal Oxides 2% EXAMPLE 13 A mixture of 90 parts by weight of Synopal and 10 parts by weight of phenolic resin is ground in a ball mill to a particle size of from 0 to 150 ,um. This binder is mixed with equal parts by weight of Synopal with a particle size of from 250 to 1500 cam. The mixture is used as a moulding composition for manufacturing roofing sheets. The sheets are pressed in a die or mould, heated to 210 C for 20 seconds. For final curing the sheets are heated with direct flames in an oven for 2 minutes. This treatment will complete the curing of the resin and burn the developed volatile gases, especially formaldehyde.

WHAT WE CLAIM IS: 1. A moulding composition comprising, in admixture, particles of a coarse aggregate and a binder therefor, wherein the coarse aggregate comprises particles of ground glass having a particle size in the range 250 to 5000m and obtained by grinding a crystallizable or crystallized glass of a type having a mass of microbubbles dispersed throughout the glass, and wherein the binder comprises an intimate blend of an organic thermoplastic or thermosetting resin and a finely-divided filler, said filler likewise comprising particles of ground glass obtained by grinding a crystallizable or crystallized glass of a type having a mass of microbubbles dispersed therein, but having a particle size less than 250 m.
2. A composition according to claim 1, wherein the particle size of the coarse aggregate is in the range 250 to 1000 ism.
3. A composition according to claim 1 or 2, wherein the finely divided filler particles have a maximum particle size not exceeding 150,um.
4. A composition according to any one of claims 1 to 3, wherein the weight ratio of said aggregate to said binder is from 1:1 to 5:1.
5. A composition according to any one of claims 1 to 4, wherein the organic resin constitutes from 5 to 10% by weight of the binder.
6. A composition according to any one of the preceding claims, wherein the organic resin is a thermosetting resin.
7. A composition according to claim 6, wherein the thermosetting resin is a phenol formaldehyde resin.
8. A composition according to claim 1, substantially as hereinbefore described in any one of the Examples.
9. A composition according to any one of the preceding claims, wherein the binder additionally contains a minor amount of a fibrous filler.
10. A moulded article comprising a composition according to any one of the preceding claims which has been compression moulded under heat and pressure.
11. A method of forming a composition according to any one of claims 1 to 9 which comprises grinding the crystallizable glass particles in the presence of the organic resin to form said binder, and subsequently adding to the binder the coarse aggregate particles.
12. A method according to claim 11, wherein the crystallizable glass particles are dry ground with said resin in powder form.
13. A method according to claim 11 or 12, wherein the crystallizable glass particles are

ground with the organic resin to form said binder in a ball mill.