WO1997007166A1

WO1997007166A1 - A process for manufacturing organic and inorganic compositions, moulded flat or extruded to give complex formation, dimensional stability, added strength, biological resistance, using non toxic resin formulations

Info

Publication number: WO1997007166A1
Application number: PCT/GB1996/001604
Authority: WO
Inventors: Derek Taylor
Original assignee: Advance Enterprises Ltd.
Priority date: 1995-08-11
Filing date: 1996-07-05
Publication date: 1997-02-27
Also published as: GB9516490D0; MY123741A; DE69636758D1; AU742095B2; BR9612852A; ATE348128T1; US6204312B1; AU6313596A; EP0824570A1; NZ311755A; EP0824570B1

Abstract

Process for manufacturing organic and/or inorganic compositions, moulded, flat, extruded or injection moulded using non toxic resin formulations such as polyurethane dispersions.

Description

PCT PATENT APPLICATION

A process for manufacturing organic and inorganic compositions, moulded flat or extruded to give complex formation, dimensional stability, added strength, biological resistance, using non toxic resin formulations.

Field of Invention.

The present invention relates to the non chemical treatment of lignocellulosics, as organic materials and inorganic materials to facilitate complex formation. More particularly the invention relates to the use of these organic and inorganic materials as compositions being pressed or extruded into finished products, giving dimensional stability, added strength, improving resistance to biological degradation, using non - toxic resin combinations. The organic materials can be in fractionated particles, none fractionated particles or fibre in homogeneous configuration.

Description of the Prior Art.

Lignocellulosics/ organic material/s posses many unique and desirable properties, it has several undesirable properties which have limited the use for many applications. It is known that the structure of the cell wall in its component parts individually and collectively determine the physical and chemical properties.

This can be seen regarding dimensional changes in respect to moisture content as the cell wall polymers contain hydroxyl and other oxygen groups and these attract moisture by hydrogen bonding. With the moisture swelling the cell wall the material expands untill the cell wall is saturated with water, water going further than this point is free water in a void structure and does not contribute to further expansion. The process is reversible by losing moisture.

Because organic/lignocellulosic materials can be degraded biologically as organisms, can recognise the polysaccharides in the cell wall and having very specific enzyme systems capable of hydrolizing theses polymers into digestible units. High molecular weight cellulose is responsible for strength in organic materials. The strength is lost as this polymer takes on further biological degradation and dehydration reactions.

Because dimensional instability and strength along with biological degradation can be said to be chemical in nature, it is possible to improve these undesirable properties by changing the basic chemistry of the cell wall polymers by encapsulation and complex formation leading to chemical bonding. Completing reaction by complex formation, encapsulation and chemical bonding precasts the cellulose and hemicellulose components as an example. The highly specific enzymatic reactions cannot take place because the moisture, oxygen and chemical configuration by encapsulation and chemical bonding has substantially altered the substrate. This chemical reaction in bonding reacts the cell wall polymers with resin reacting chemicals and reduces the tendency to swell to an absolute minimum, and this when subjected to change in moisture because the lignocellulosic in organic materials is chemically swollen and reaction encapsulation by application of heat.

The hydroxyl groups therefore play a significant role in the organic and inorganic applications of the resins to produce the end product.

Organic materials as lignocellulosics and inorganic materials fractionated and blended with themselves and together. Resin systems greatly improves dimensional stability and bond strength and is resistant to biological attack and is according to the invention, made in the absence of any co solvent or added catalyst and does not use combinations of urea formaldehyde resins or phenol resins and made in a simple way.

Partially dry or dried organic or inorganic materials or combinations of both are fractioned or unfractioned and blended with non toxic resin systems to give complete envelope and complex formation. The material is then dried, pressed, moulded, or extruded into finished items in a short period of time.

It cannot be stressed enough that the invention deals with aqueous resin application in liquid, solid dispersion and then dried

Moulded Compositions - Organic and Inorganic

Description of the Invention.¹

This invention relates to mouldable compositions in organic and inorganic materials used in combination or singularly which may be used for very many applications and in particular a substitute for wood in organic material and utilisation of waste inorganic products for substitute to natural building and construction materials.

The desirability to reduce the world usage of wood is well known and many products are available, which can serve as substitutes for wood in some types of application.

The realisation and utilisation of such materials collects multiple organic and inorganic materials usage as forest grown or horticultural/ Agricultural grown to wastes of such materials as a biomass as starter materials also inorganic materials in their natural state or as waste materials as in multi purpose configurations.

Such materials as listed but not confined to have been used to produce finished products giving enhanced value and multiplicity of use.

1) Hard Wood Dust

2) Rubber Wood

3) Softwood Flakes

4) Hemp Fibre Dust

5) Semphire

6) Salicornia

7) Bagasse

8) Rice Husk

9) Ground rice

10) Palm - Fronze- Bunch, Trunk

11) Paper

12) (1-9) As flour

13) Cloth

Used singly or in combinations. Inorganic Materials

1 ) Slate Dust

2) Ceramic Dust

3) Pottery Waste

4) Dune Sand

5) Sea Shore Sand

6) Quarry Waste

7) Limestone

The above being used as single materials or in combination and in combination with other materials.

Some of these basically comprise reconstituted wood, whereby wood residues are applied into a homogeneous mass to form a solid product, which have many of the properties of wood.

Chipboard is an example of such a product, however, chipboard and similar products are only available in the form of flat boards and the manufacturing process by which such products are obtained does not lend itself to the production of shaped sections or mouldings which are required for many architectural features in the construction of buildings for example. Such shaped components, which were traditionally formed from solid wood by appropriate machining operations, are often replaced by equivalent components made from metal or from plastic materials, but such materials are generally environmentally disadvantageous with regard to such matters as the energy expanded in the production of the raw materials, and often the hazardous nature of the chemicals required for processing.

On the other hand the organic and inorganic materials listed offer vast quantities or relatively innocuous waste vegetable matter arising from numerous industrial processes -similar occurs with inorganic material as listed. All of these materials having little or no commercial use at the moment.

The object of this invention is to provide a novel mouldable composition in organic and inorganic materials, polymeric in nature, homogeneous in finish for use as a substitute or combination composites of low toxicity, low hazard, high stability and inner bond strength. According to a first aspect of the invention we provide a moulding composition, homogeneous in structure comprising of organic or inorganic fractionated materials singularly or in combination, coated with a fully reacted high molecular weight polyurethane resin. Resin modified with hydrophilic groups such that the coating is not penetrative absorbent to the particles of the fraction.

From the outset it should be noted that the resin compositions exclude totally the use of;

1 ) UF Resins

2) FMUF Resins

3) MUF Resins

4) Isocyanate Resins

5) Phenolic resins - Resoles or Novolaks

According to the second aspect of the invention we provide mouldable compositions homogeneous in structure from the following types of resin for both organic and inorganic materials.

1 ) Polyurethane combinations

2) Acrylic combinations

3) Hybrid combinations

4) Compositions of resins synthesised from palm oil source.

5) Compositions of resins synthesised from salicornia oil source.

6) Compositions of resins synthesised from dextrose mono hydrates

According to the third aspect of the invention.

The above (1-6) giving complex formation of the substrate homogeneous material.

According to the fourth aspect of the invention all resin combinations become thermo plastic at first temperature above ambient so that the resin flows affording the composition to the encapsulated and capable of consolidation into a shaped mass. The resin furthermore becoming thermosetting at a second temperature, so that the shaped and consolidating mass in organic or inorganic or combinations become rigid and irreversibly shaped. According to the fifth aspect of the invention the modified resins (1 - 6) as employed are preferably in the form of water based dispersions in which hydrophilic ionic groups area attached to the polymer back bone. Such hydrophilic ionic centres function as internal emulsifying agents and the resin does not contain any free Isocyanate.

The process for manufacture of such colloidal urethane resins begins with reacting a polyether or polyester-diol with an excess of diisocyanate eventually in the presence of a small amount of solvents. By selecting proper polyol/diisocyanate ratio's, a lower molecular weight, high solids prepolymer is thus prepared. In addition, carboxylic acid functionally is reacted into the backbone by using an acid diol or dihydroxy acid.

After neutralising the acid groups with a basic material such a tertiary amine. the prepolymer is added to water under agitation, forms an emulsion, and is further extended with e.g. a diamine. The resulting urethane dispersions can be classified as colloidal due to their fine particle size (less than 0.1 micron) when the concentration of ionic or hydrophilic groups in the polymer backbone allows the achievement of small particles.

Whilst the resin is in dry form with no increase in temperature beyond pre-determined limits the resin remains thermoplastic, but when heated beyond a pre-determined temperature the resin quickly becomes thermoset.

During the curing of such urethane dispersions there probably occurs a certain physical cross linking caused by:

- elecrostatic forces between hydrophillic groups (Colombo forces).

- hydrogen bonding between urethane groups.

- interaction between hydrophobic segments of the chain (association).

The physical cross linking is partly responsible for the excellent properties of the cured material. Further resistance improvement is achievable by using additional cross linkers of which the polyfunctional aziridines are most commonly used.

The ionic nature of the backbone also allows the use of other cross linking systems such as melamines, expoxies etc.

We further can use an improved method of binding by using acrylic-polyuerthane dispersion.

To obtain a storage stable acrylic- polyurethane dispersion, the emulsification and/or dispering mechanism of both polymers must be compatible within the desired pH-range, usually between 7 and 8. The most simple combination is physical blend. In general, these coatings have an improved stain and abrasion resistance.

This technology can be applied to produce one-component, low VOC, storage stable, self-crosslinking adhesives and resins.

An aqueous dispersion of such modified urethane and/or acrylic resin can be added to organic and inorganic matter and combinations, so as to envelope each individual particle and produce a flowable composition which can be fed into various forms of moulding and extrusion apparatus.

It is according to the sixth aspect of invention, aqueous dispersion resin of compositions as listed in conjunction with particle modelling for fractionation of composite organic and inorganic materials to precise limits is essential for flowable composition.

During the passage of the composition through such equipment its temperature can be maintained within the range in which it remains thermoplastic, there by improving its flowability, until the material reaches the designed degree of compression and shape for the article to be produced, whereupon the temperature can be increased to such a level at which the composition becomes thermosetting and held at that temperature until substantially fully cured.

It is according to the seventh aspect of the invention that further enhancement can be achieved by the use of water repellents synthesised with resin structure, this giving month on month stability to the end product/s and giving such a product/s engineered hydrophillic and/or hydrophobic properties suitably enhancing range of end product uses, enhancing performance possibilities of empirical attachment or stand alone repellent materials can be utilised.

Combinations include but not confined to:- Hydroxyl Siloxane combinations as preparations.

Hydrogen Siloxane combinations as preparations.

Amino Functional Siloxane combinations as preparations.

All with compatability to resin pack with CPUs 50-2000 in combinations as synthesised liquids and emulsions with and without additional dilution characteristics, as well as dispersions and 100% liquid solids.

The organic and inorganic materials comprise waste residues of materials as listed the materials can be used damp or dry.

Tests have established that particles need not be separated to produce a quality product. To obtain a storage stable acrylic-polyurethane dispersion, the emulsification and / or dispersing mechanism of both polymers must be compatible within the desired pH-range, usually between 7 and 8. The most simple combination is a physical blend , as used today in the coating industry. To obtain an acceptable level of solvent resistance (e.g. ethanol) the use of an external crosslinker is necessary.

When both polymers consist of a crosslinked network, an Interpenetrating Network (IPN) is formed: the chains of one polymer are completely entangled with those of the other polymer. Such IPN's are more stable than physical blends because they show less phase separation.

A more complicated approach involves the chain extension of the polyurethane in the presence of an acrylic resin, or even the reverse; emulsion polymerization of acrylic monomers in the presence of a polyurethane. This results in a new hybrid system with an increased solids content since one polymer is diluting the other while it is being synthesised.

Recently, much attention has been focused on the development of aqueous polyurethane and acrylic copolymers because of their improved computability, weatherability and film forming behaviour. However this copolymer technology cannot reach the same performance level as fully crosslinked systems.

In order to take advantage of the respective physical and chemical properties of acrylics and polyurethane's, and at the same time overcome their specific drawbacks, both polymeric structure can be combined into one single, self-crosslinking composition. In such hybrid systems the acrylic portion of the polymer imparts hardness and good ageing properties into the coating, the polyurethane portion brings enhanced film forming characteristics, elasticity and abrasion resistance. These new hybrid systems are storage stable: crosslinking only takes place during the coalescing phase in a drying film, and reaches the maximum crosslink density after 3 days at 20C. or indeed decreased time of crosslinking is possible with increase temperatures, i.e. between about 60C. and 300C. Increased solvent and water resistance occurs after water evaporation as a result of interfacial crosslinking through built-in functional groups located on the surface of the polyurethane particle, and propriety reactive groups copolymerized into the acrylic backbone and which are buried into the core of the acrylic phase. This explains the stability of the acrylic-polyurethane dispersion.

Although the crosslinking mechanism is not yet fully assessed it may be assumed that the reaction is made possible due to a molecular interdiffusion process. This mechanism of formation of a cohesive film via interdiffusion of polymer chains across the original boundaries has been recognised as a basic concept for mechanical strength of films made from emulsions.

Evidence for the self-crosslinking can be found in the improved solvent resistance and increased gel content, the increased softening temperature and the appearance of a single Tg. According to the eigth aspect of the invention curing is rapid and its possibilities to mould and shape a board 8' x 4'(feet) and weighing 40 kilograms in under 120 seconds, typically 90 seconds. The shaping in both organic and inorganic materials being carried out at temperatures in the range of 70*C to 90*C and the thermosetting at temperatures above 120*C. whilst flat faced sheets or boards in organic or inorganic materials can of course be formed from the materials to produce a density water proof board with pigments fire proofing agents, and resin forcement such as carbon fibre, included in the composition is also suitable for forming by moulding into complex shapes or by extrusion into continuous lengths of complex cross section.

It is particularly to be noted that the composition after initial compression at said first temperature, forms an immediate material and that it can be stored and transported in a safer manner and without the restraints of wood. Again in the same way that for example lengths of timber can be shaped by appropriate machine operations as and when required.

Intermediate material can also be shaped as and when required by subjecting it firstly to heat such as to raise its temperature again into a range at which it becomes flowable.

applying pressure to form it into the desired shape whilst at such temperature, and finally raising the temperature to cause thermosetting to occur in both organic and inorganic materials and in combination of both.

According to the ninth aspect the invention also resides in a mouldable article formed from organic or inorganic or combination materials which has been compressed and shaped at said first temperature to form a storable rigid product.

The mouldable article may take many forms. In one case the article may comprise a flat panel or board, such panel or board in thickness 2.5mm to 40mm can then be embossed on one or more surfaces for example to produce door profiles or wood grain, or with various decorative figures. Alternatively the panel or board can be reshaped, for example to a curved form, with or without surface moulding or embossing. After such operations carried out at said first temperature, the temperature is raised to cause the material to thermoset so as to form a rigid shaped product, which may for example compromise a decorative door panel, an architectural moulding, a skirting board, and architrave etc. Fittings such as hinges, handles and the like can be incorporated during the shipping process and be screened directly into composite meeting DSTM requiremnts, so as to become firmly bonded during thermosetting of the material.

In another case the mouldable article may be formed as a solid or hollow bar or rod which can subsequently be shipped by extrusion to form a shaped beam, column or the like. In a further case the mouldable article may be formed as a block or a brick, or a brick which can subsequently be shaped by standing or the like to form a shaped solid body.

It will be recognised that conventional pre-constituted materials cannot be processed in this way.

Alternatively, of course, the composition in accordance with the invention in organic or inorganic or combination materials, can be formed into a finished article directly without being formed into a storable intermediate article and again sawdust organic/inorganic materials can be stored in silos or stored in covered areas for multi purpose usage.

The whole of the invention in finished flat and finished mouldable products meets and surpasses requirements of

BS 5669

BS 1 142

JISA 5908 For stability. and BS 5669

BS 1142

JISA 5908 For internal bond strength (IBS) in all climatic conditions.

In respect to internal bond strength before climatic conditioning, IBS can be engineered with finished tensile strength from 0.4MPa -4.5MPa for each thickness 2.5mm-40mm and after climatic conditioning i.e. boiling and cyclic testing for 2 hours duration over 24 hour period, maintain 92-98% of properties and strength characteristics following further bond strength testing. With water repellence the same results apply with the additional or controlled water ingress per mm over 24 hours to maximum engineered ingress per board per thickness.

Fire Testing.

The board from 2.5mm to 40mm thick will meet BS476 - parts 20-22.

Surface Spread of Flame.

Standard boards can have class 3 surface spread of flame as BS476 part 7 1987.

Effect of relative humidity change from 65% to 85%.

Increase in length - less than 0.1%

Increase in thickness - less than 2%

Water.

Homogeneous board is suitable for internal and external use in areas with prolonged wetting exposure.

Insect Attack.

Infestation proof temperate climates

Infestation proof tropical climates. Under test.

Fungal resistance

Will not rot or be attacked by wet rot fungi under prolonged conditions

Working Characteristics - Health and Safety,

Homogeneous particle board can be cut by hand or power saw and machine (routed, spindled, planed and bored, on edge,) with normal woodworking machinery. Tungsten carbide tipped tools are recommended for use with powered tools.

Ecoboard will generate dust when machined.

Regulation 7 of the control of substances hazardous to health regulations (COSHH).

requires that exposure to dust is either prevented or, if this is not realistically practicable, adequately controlled. The current occupational exposure standard for softwood dust would apply in all cases where lignocellulosic products are used as basic starter material, 5mg/ m₃, expressed as an eight hour time waited average. Hard wood dust as applied is listed in Schedule 1 of COSHH, and is therefore a maximum exposure limit. The value for hardwood dust is also 5mg/m₃ .

Advance Enterprises Limited recommends that dust extraction equipment to meet COSHH, be installed and adequately maintained along with dust masks and safety glasses all should be used when working with any lignocellulosic based material. For further data see Health and Safety executive information sheet (selection of respiratory protective equipment suitable for use with wood dust. Woodworking sheet 14). For other materials please consult Advance Enterprises Limited.

Formaldehyde/ Phenol Content.

Advance Enterprises recognises wood contains a minute amount of formaldehyde but also states that no formaldehyde release whatsoever is experienced using the AEL products whether looking for formaldehyde or phenol. No leaching of residues throughout the whole of climatic testing. Effluent is European domestic grade.

Application.

Flat board products

Moulded products

Extruded products

All product are for use in external and internal conditions ie. doors, window frames, soffits, floors, roofs, barge boards, flooring , LD & HD. The Ecoboard product is multi purpose in its use and can be reduced for all applications where polymeric materials are used today and can go a long way to replace metallic veneers and high grade polymer applications.

Advance Enterprises Limited Ecoboard is the new multi-purpose polymeric material for the nineties and bevond.

Size.

Board sizes 2400mm × 1200mm. combination cutting to order a possibility.

Weight.

Typical densities 630, 650. 690. 720, Kg/ m₃ giving board weight atl6mm of approximately 20/33 Kilos.

Climatic Effect.

Ecoboard is not hygroscepic and its dimensions do not change above 4% after testing in two hour cycles at 95% RH at 95*c. Enginereed property retention - 100%, as required. Material becomes polymeric in nature.

Behaviour in Use.

Quality levels given below, should be used for reference and design purposes. Specific values can be engineered for specific products to customer request by simple manufacturing menu adjustment.

T

Figures 1 to 6 illustrate by way of example various ways in which the material may be shaped.

FIGURE 1 illustrates compression moulding in which the material is charged into the bottom die, and the top die is then closed to impart the required shape to the material which is held at the required temperature for a predetermined cycle time, after which the press opens and the finished moulded component is ejected;

FIGURE 2 illustrates transfer moulding carried out in a similar manner;

FIGURE 3 illustrates injection moulding;

FIGURE 4 illustrates a conveyor press in which the material is fed onto a conveyor belt which advances intermittently, and while the belt is stationary, the material is compressed by a heated platen to the required thickness and held under compression at the required temperature for the appropriate length of time for curing to occur;

FIGURE 5 illustrates a process of continuous extrusion on a conveyor belt. In this case, the material is delivered to a continuously advancing conveyor and passes through a succession of heated rollers. Alternatively, or additionally heat may be applied to the material in any appropriate manner between the rollers. The final roller may be embossed to provide any appropriate pattern on the finished material, for example simulated wood grain.;

FIGURE 6 illustrates an extrusion process to produce a continuous length of solid material of any required cross-sectional shape.

The raw material, i.e. waste vegetable matter together with any fillers, extenders, fireproofing agents and pigments is advanced along an inlet of 10 and into and through a first heating section 12. The resin dispersion is introduced at 14, upstream of the heating section 12, and mixed with the incoming material in the heating section whilst the resin is in a thermoplastic condition. The thermoplastic material then passes into a compression section 16 from it is displaced by means of a piston 18 through a forming die 20 into a heating outlet area 22 at which the temperature of the material is raised so that it becomes thermosetting. The length of the heated area 22 is such that the time required for the passage of the material through the area is sufficient for the material to thermoset.

It is to be noted that the necessary heating of resin can be carried out in various ways including induction heating high frequency, microwave or infra-red heating or by the application of ultrasonic energy, as well as electrical resistance heating.

The features disclosed in the foregoing description, or in the accompanying drawing, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, may, separately or in any combination of such features, be utilised for realising the invention in diverse forms thereof. These coatings have improved stain and abrasion resistance.

The technology can be applied to produce one component, low VOC, storage stable, self-crosslinking adhesives and resins.

Claims

1 ) A process for manufacturing organic and inorganic compositions, moulded, flat or extruded. To give complex formation, dimensional stability, added strength, biological resistance, being able to be used internally and externally, using non toxic resin formulations. Characterised by the following steps. a) Providing the material is suitably blended and dried (b) moulded composition homogeneous in structure, comprising organic or inorganic or combinations as fractioned materials (c) utilising fully reacted high molecular weight polyurethane resins (d) resin modified with hydrophilic grounds such that coating is not penetrative absorbent to particles of the fraction, (e) very low volume resin use (f) non toxic resin formulations (g) minimum timing to form finished article (h) further enhancement using synthesised water repellents.

2) A process according to claim 1 characterised by (b), (c), (d), (e), (f) mouldable

compositions homogeneous in structure organic/inorganic or combination using

polyurethane combinations

Acrylic combinations

Hybrid combinations

Compositions synthesised from palm oil

Compositions synthesised from salacornia oil

Compositions synthesised from dextrose mono hydrates.

3) A process according to claim 1 and 2 characterised in (c), (d), giving complex formation of the substrate as homogeneous material.

4) A process according to claim 1 and 2 and 3 as characterised (c), utilising resin combinations becoming thermoplastic at first temperature and thermosetting at second temperature.

5) A process according to claim 1 and 2 as characterised in (c), (d), utilising water based dispersions in which hydrophilic ionic groups are attached to polymer backbone.

6) A process according 1 and 2 and 3 as characterised in (a), (b) aqueous dispersions in conjuction with particle modelling for organic and/or inorganic materials and its combinations giving flowable compositions.

7) A process according to claim 1, 2, 3, 4, 5, 6 as characterised in (1) giving further

enhancement utilising synthesised water repellents in combinations using hydroxyl siloxanes, hydrogen siloxanes amino functional siloxanes in synthesised liquids, in combinations or liquids and dispersions with and without additional dilution characteristics, dispersions and 100% liquid solids.

8) A process according to claims 1, 2, 3, 4, 5, 6, and 7 as characterised in(g) rapid curing of fiat, extruded and moulded products.

9) A process according to claims 1, 2, 3, 4, 5, 6, 7 and 8 as characterised in (a), (b), (c), (d), (e), (f), (g), (h) organic, inorganic or combination materials in flat extruded or mouldable item in varying thickness and densities becoming thermoplastic at first temperature and thermoset at second temperature. 10) A process according to claims 1, 2, 3, 4, 5, 6, 7, 8 and 9 as characterised in (a), (b), (c), (d), (e), (f), (g), (h) that testing of materials surpasses BS5660, BS1142, JISA5908, DIN, for stability and BS5669, BS1142, JISA5908, DIN for internal board strength (IBS) in all climatic conditions including V313 with engineered 90-100% property retention.

11) A process according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 as characterised in (a), (b), (c), (d), (e), (f), (g), (h) meets fire testing 2.5mm to 40mm thick to BS476 parts 20-22 and spread of flame to BS476 pack 7.1987.

12) A process according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 as characterised in (a), (b), (c), (d), (e), (f), (g), (1) has no formaldehyde or phenol release, no leaching, effluent is domestic grades.

13) A process according to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 as characterises in (a), (b), (c), (d), (e), (f), (g), (h), (1) whereby, the aqueous resin is applied and dried and can be stored indefinitely prior to being used for manufacturing purposes, organic/ inorganic/ combinations of organic and inorganic. Including cloth.

14) A process according to 1, 2, 3, 4, 5, 6, 1, 8, 9, 10, 11, 12 and 13 as characterised in(a), (b), (c), (d), (e), (f), (g), (h), (1) whereby the resin systems applied can produce flat boards thermo laten which can later be shaped into thermo sets.