JPS61283439A - Manufacture of molding substance containing water glass - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Applications It is known to make molding materials containing water glass. In this application, "molding material" refers to any moldable or plastic material. Although these are preferably formed by casting, they may be formed by other methods such as pressing, rolling, etc.
In many cases, it may be molded into the final product. Molding substances of this type have many applications, for example in the manufacture of various objects, and can also be used as adhesives between surfaces of different types. In the production of molding materials of this type, which are known in the widest possible terms with respect to their scope of use and working methods, a step is carried out to reduce or eliminate the amount of water in a concentrated solution of water glass in the form of an alkali silicate. My friend is using it. In this way, "water glass quartz J" is often used.
A solid product called squartz is obtained and is made by drying liquid water glass or changing its pH value completely by adding acid to neutralize the alkaline state. That is, sodium hexafluoride is added as a hardening agent,
This condition results in water consumption and also affects the pH value of the formulation.

This type of molding material is formed into a more or less uniform product by adding other materials, such as the well-known Quoru powder (8102), during or just before its curing; in this case, the added material The particles are bound together as water-reduced inclusions by water hyaline liberated from the water.

Water glass exists as a sodium silicate and a potassium silicate, but ultimately exists as a mixed silicate of sodium and potassium.

Water glass made from ammonium is also known, but it has little practical use. Sodium water glass is the most common and therefore will be discussed as a sodium water glass basis in the detailed description of this invention.

However, this does not mean that the invention is limited to this particular type of water glass.

Products made from this molding material have very high wear resistance. When used as an adhesive, it adheres very well to most materials and can be used on many materials to which conventional adhesives do not exhibit adhesion properties. In addition, although the product has strong tensile and impact stiffness, no integral relationship is seen between these 5@ stiffnesses, except for the fact that the increase in pressure stiffness is the most significant, and only the impact stiffness increases. is relatively small.

Several methods are also known for the production of molding materials of the above-mentioned type with improved properties by the addition of other additives to improve the properties of these materials.

OBJECTS OF THE INVENTION The present invention relates to a process for the production of molding substances in the above-mentioned sense and to products of the above-mentioned type, and in particular to further improvements in the properties of molding substances, including the formation of crystals within the substance produced by reaction. It relates to obtaining a molding material that is less sensitive to the amount of water in water glass than before.

The molding materials made in accordance with the present invention also allow for a wide range of variations in conventional additives to obtain a good distribution of the particular properties sought to be achieved with the additive.

〔problem? According to the invention, silica is added to the known molding material, preferably in the form of crystalline powder or grains, in the amounts to be revealed below.

Silica (5i1ika) is a high molecular weight silicon compound in which this silicon is converted into carbon or chemically converted into carbon by rJ.
It is the conventional name for pure i-form silicon or some simple compound made by applying high power to make silicon chemically active in a way that makes other elements in the R group chemically active.

Although it is not completely clear how to explain this "activity," one theory that is believed to be correct is that one or several electrons in active silicon deviate from their normal orbits and move inside the molecule. It moves in such a way as to generate stress, and when it is released, a considerable amount of energy is released. Under the influence of this Ni Energy, activated silicon generates chemical reaction sounds, which in non-activated silicon and silicon, only total heat or extreme values exist. This energy supply is usually achieved by heating the silicon compound at very high temperatures. As a result, we find a very high proportion of highly activated silicon in the fly ash of the steel industry, due to the high temperatures present in this location.

When active silicon is added to the molding material, this changes its properties in such a way that there is good reason to believe that metal phase chemical reactions take place as is often the case in silicate chemistry. However, I do not know how to explain this reason. However, although it is clear that the reaction occurs within the scope of silicate chemistry, this is difficult to understand and remains largely a mystery. Accordingly, the present invention is made purely empirically.

An important advantage of the molding material of the present invention compared to previously known water glass-based molding materials is that the range of various additives increases considerably with the addition of quartz (8,102). It is.

In testing this type of component, the effects of the addition of micronized cellulose alone to water vitreous and water vitreous mixtures were fully investigated, which revealed a number of situations that have so far only been observed experimentally. However, these form the basis of a preferred experimental implementation of the invention. These four researches were carried out in the following way: First, in order to obtain a product that can be used in most cases and can be produced at a very low cost because it is an inexpensive diluent, cellulose was added in the form of micronized holes as a diluent. I decided to investigate whether it would be possible. Surprisingly, the products have been found to have unexpected and, in many cases, very useful properties.

The addition of neutral or basic cellulose has been found to be of little use; however, weakly acidic cellulose can impart the above-mentioned properties to the final product or provide acidic properties to the molding material after mixing with finely divided cellulose. A study was carried out to determine the type of acid and it was found that bark powder produced very good results. Bark powder contains small amounts of tannic acid.

Furthermore, very good results have been obtained with the use of so-called zero fibers, ie cellulose fibers so fine that they pass through the wire during dewatering and are removed with the waste water. These fibers always contain certain residues of one or more acids for cellulose treatment, firstly sulfurous acid and other acids. Generally, these acids occur in very small quantities, or even if they occur in large quantities, their activity is weak, as in the case of tannic acid and sulfurous acid.

An important improvement of the present invention is therefore that water glass and silica (s)
It consists of adding an acidic cellulose material in finely divided form to a mixture with ilika) in an amount close to 5 to 75% by weight of the total weight of the mixture, as determined by experiments. .

In the above-mentioned practice, it has been found that various plastic emulsions in the form of uncured or partially cured combinations can be added to the molding material of the invention. These cures or the completion of the cure that has been initiated are carried out simultaneously with the cure of the mold ink material after the addition of the curing agent. In this way, a large number of different new products are obtained, which have the properties of polymeric products in a quantitative sense, but which have considerably improved properties in a qualitative sense. Other additives that should be mixed in include the following:

Molding substances can also be made by the addition of bulk positive materials, especially heavy metals in the form of powders, particles, etc. Among this kind of metals should be mentioned together with lead and copper and alloys containing lead and/or copper, such as bronze and bronze. Will. The ability of the molding material to accumulate heat is therefore very large. The conduction of heat supplied to the molding material and the removal of accumulated heat from the molding material are each simultaneously improved, reducing the unavoidably necessary time consumed for supplying and removing a given amount of heat.

Furthermore, the molding material maintains its rigidity and can be expanded while remaining solid to a greater degree than is conventionally possible, and this expansion can be accomplished in a variety of ways. For example, some suitable tenside may be incorporated into the material in the presence of air, or some plastic that expands under the influence of heat, such as polystyrene or polyurethane, may be added to the molding material and then Heat this all up completely before it hardens. For example, a suitable temperature for the addition of polystyrene is 90°C.

As mentioned above, it is also possible to mix a finely powdered cellulose material in an acidic state. When the advantages resulting from this are not evaluated, a cellulosic substance in a basic state can be mixed. In this case, the cellulosic substance, preferably Zero7 IPA, is added to the molding material of the invention together with a divalent carbon salt, preferably at a slightly weaker concentration by the addition of plastic.

Not only can various plastics be mixed in the molding material of the present invention, but also other materials such as latex can be added to the asphalt, preferably when said material is in an emulsion state. . Said material gives the molding material good properties as an adhesive.

Because of its improved adhesive properties when used as a molding mass adhesive, it is also particularly well suited for reinforcing purposes. Such reinforcement can achieve good results with reinforcing materials previously considered unsuitable. The very low cost of these reinforcing materials allows products to be supplied at very low prices compared to previously known reinforcing materials. When using the molding material according to the invention, hardening begins from the outer surface of the material, just as a skin surface is formed, which is plastically shapeable, and the interior of this epidermal layer can initially be shaped to a considerable extent. However, it retains the ability to maintain its shape afterwards. Thereafter, by pressing, rolling, etc., a quantity of said material is given a predetermined shape, which is then maintained during the continuation of curing. This fact can be used, for example, when pressing a putter 7 or a relief onto the surface of the material of the invention.

Particularly noteworthy among the advantages of the present invention is that when used in the same manner as conventional water glass-based parts, such as covering parts of buildings with a fire hazard, it becomes a good fireproofing material. ,That's what it means.

Therefore, the structure of the building coated with the molding material according to the invention, 1111 parts, can be coated with a large amount of normally fire-hazardous materials such as sawdust, peat, other organic materials or asphalt emulsions without impairing the fire protection properties. The fire-retardant properties of the molding material according to the present invention also make it possible to use the molding material of the present invention for laminate materials, especially for architectural board materials, for which various glues with weak adhesion or flammability have traditionally been recommended. This also arises from the fact that it is suitable as an adhesive for manufacturing.

Silica (5iIika) A friend who has carried out considerable research to investigate the amount of silicon, either in pure form or as a simple compound, relative to the amount of water glass to which quartz may be added. This allows silica as Si (5illk
A special addition to the water glass composition of the invention in the addition of silika in a proportion or weight ratio of between 6 and 5% of the dry weight of the sum of silicon, water glass and occasionally added quartz in a). It turns out that the property gives money. The amount of silica should not be less than 6% by weight, because it is not sufficient to exhibit the above-mentioned advantages, and conversely, the amount of silica should not be less than 6% by weight.
or less, since in this case the stiffness is lower than without an excess of silica and there is no significant improvement in the above-mentioned properties of the molding material.

Fine cellulose, especially Zero 7 from the paper and pulp industry
In the above-mentioned tests regarding Ivano addition, it was found that although mixing in the clay-based state is certainly advantageous for certain purposes, it is unfavorable for other purposes. However, it has also been found that the addition of cellulose material under acidic conditions in the manner described above also yields very good results.

This type of blend does not adversely affect the fire resistance and still retains its full flame resistance. In the case of small additions of acidic cellulose, strong soot formation is observed when exposed to a weak flame, but as m of cellulose is increased, the product becomes completely flame resistant and cannot be combusted by an external fire as described above. Even if this occurs, combustion will stop immediately when the source of fire is removed.

Another cosmetic feature of the product is its elasticity, but this does not appear to affect its tensile stiffness. Products with high elasticity and shapeability without fear of breakage will find many different applications that were previously unavailable to cheaper materials.

The most important characteristic of the product is its low manufacturing cost. It consists primarily of materials that were previously considered not only to have no use, but also to be hazardous and unusable for any useful purpose. Therefore, finding useful applications for these materials should be considered highly desirable. It is this type of application made possible by the present invention. Furthermore, the final product is one that does not require high costs and at the same time obtains good properties. In fact, it can be produced cheaply.

In the investigations forming the basis of the present invention, it was found that the acidity (pH) of the cellulosic material used was of decisive importance. If the value of pu is too small, the above-mentioned advantages will not be exhibited in the product made from the molding material, and the pH
If the value of is too high, the curing will be too fast and there will not be enough time to fully control the flow of the product, and the resulting molded product will be brittle and easily damaged. Thus, clearly it is not difficult to choose a value of p such that curing occurs as slowly as is required for reasonable production, but it is not acceptable. An accelerator can be added to the curing agent; As promoters of this type it is preferred to use suitable phosphorus compounds, such as ammonium phosphate.

Furthermore, in making products by adding cellulosic materials in acidic conditions, curing can also be caused by alternating current flowing through the molding material, making it a very effective means for controlling the curing rate.

Further research was invested to discover the pH limit of acidic cellulose. These investigations revealed that the pH value must be between 2 and 6. If the pH value is below 2 or above 6, a complete product cannot be obtained; this is usually unusable.

Good results are readily obtained when mixing cellulose material in the form of Zero 7 Ipa from Sulfuric Acid Industries.

On the contrary, certain difficulties arise when collecting Zero 7 IPA from the sulfuric acid industry. As a matter of fact, Zero 7 IPA from the sulfuric acid industry is usually very acidic when it leaves the wire, and is then certainly within the limits of the pH values mentioned above, whereas the above substances are usually not in this state. The reason for this difficulty is
Zero-fiber material has traditionally been considered a hazardous substance, and therefore it is flushed away from the outlet with the waste water from the hot water channel heir, which can lead to acidification of the waterway and sometimes to that of the groundwater. This is considered a danger to the environment and legislation has been promulgated requiring zero fiber materials to be de-acidified, for example by the inclusion of lime (CaO) in certain internal reservoirs.

By this process, however, the zero-fiber material g from the cellulose industry, in particular from the cellulose sulphate industry, obtained on the market for the purposes of the present invention, with respect to its pH value:
This results in an outside of the limit value that is supposed to be maintained by the present invention.

Therefore, this drawback must be addressed before adding zero fiber material to this type of molding material. In practice, this is done by acidifying the zero fiber material before adding it to the water glass.

This is done by adding a suitable acid; in practice only sulfuric acid is used here.

Zero-fiber cellulose from Sulfite Pulp Industries could also be used, although Zero 7 IPA from Sulfite Pulp Industries has been found to be slightly better. However, the latter is strong sulfuric acid (
(H2SO4), the acidity requirement is sometimes too high. However, while it may be used for certain purposes, it is not intact when it is collected directly from the wire, in which case it should be deacidified.

The type of cellulose material added is not critical. The reason for mentioning specifically zero-fiber materials from the cellulose industry, and first those from the sulfuric acid and sulfite pulp industries, as mentioned above, is simply that this material is an unwanted by-product and therefore its effectiveness is limited. This is because its use has the added value of reducing pollution.

Another unwanted waste product is tree bark, although the pollution caused by bark is of only secondary importance, since bark naturally decomposes into mulch.

However, bark is another substance for which we would like to find a useful use.
To this end, research was conducted on the creation of the present invention using finely powdered bark. Bark flour has some tannic acid when taken from golden pine trees and corresponds relatively well to the requirements of the present invention. Therefore, pH adjustment is usually not necessary.

The amount of cellulose-like material added can be varied within fairly wide limits, such limit values being expressed in units of 5 to 75 parts by weight, which are based on the dryness of the total mass contained in the composition. As mentioned above, it was calculated based on. This change in the amount of cellulose causes a large change in the properties of the material produced. The small content of cellulose is
Contrary to expectations, the rigidity of the product was low, but at the same time a very light product was obtained, and a product with a large elastic restoring force against changes in shape was obtained. As the initial material based on water glass increases, the stiffness gradually increases, but the elastic restoring force of the shape decreases, but only gradually. Even at the highest content of cellulosic material of the promised 75% by weight, the elastic restoring force is quite strong.

Of course, the more initial material striations are included in the product, and the less bulky the cellulosic material, the heavier the product will be.

The above-mentioned properties of the product made from the composition according to the invention show that the composition can be usefully used in the manufacture of various articles. It is made by introducing heavy metals such as copper or lead. Both lead and copper are relatively expensive, but at the cost of efficiency they can be used to store heat ``a'ff: When cheaper and more productive, these metals can be replaced by materials in the group commonly referred to as ``brown materials.'' are used, but some of these materials include soapstone, feldspar,
There are serpentine, olivine, etc.

The compositions according to the invention are furthermore particularly suitable for the production of building materials in the form of boards, such as gypsum boards, coke slag boards, etc., which have traditionally been used. The application of the molding material according to the invention is not limited to this field of use.

Regardless of whether cellulosic substances are used or not,
Further, even if a cellulose-like substance was used, tests were conducted on the addition of various polymeric products, regardless of whether it was alkaline or acidic. This allows us to identify any kind of material as a type with the purpose of imparting specific properties to the final product.
It has been found that the above-mentioned advantages exist regardless of whether or not all compound products are used. In these tests, however, it was possible to observe strange things for which no reliable explanation could be found. The water glass composition according to the present invention contains 2
By adding a predetermined proportion of polymerized products of different types, such as phenolic resin and acrylic resin, or epoxy resin and acrylic resin, it is possible to obtain not only the qualitative properties but also the quantitative properties of the combination of the two companies' gold products. You get a final product that appears stronger.

For example, the water glass composition of the present invention can be used to improve all of the properties of the gold acrylic resin and the properties of the epoxy resin, but when both are added, gold is added to only one of the two resins. The stiffness of the composition also allows a product with considerably greater stiffness to be obtained. It was impossible to find an explanation for this, but the cross-link between both resins may be water glass.
More likely, it appears to be due to generation under the influence of silica;
ilika) has potential and would therefore be recommended as an activator/catalyst. Quartz, if present, may also participate in this possibly catalytic reaction. This last story is somewhat questionable.

Therefore, the investigation continued until two polymerization products of this type were selected, but due to the precise and detailed characteristics of each polymerization product itself,
It was believed that the most reliable results would be obtained if the investigation was carried out on the basis of adding acrylic resin gold to the water glass composition of the present invention in combination with an epoxy resin. As a result, stiffness values were obtained, but although there were some uncertainties, only one of the two resins was about 40 times higher than the value obtained by adding the entire water glass according to the present invention. value was obtained. The reason why the stiffness value was slightly uncertain is 1.
This is thought to be due to the fact that the test was conducted without making resin particles of the same shape and size, but this uncertainty is thought to be due to the environment at the time of practical use.

This phenomenon is particularly well observable in the range between IJllo and 60% of the acrylic resin and between 10 and 60% of the weight of the epoxy resin, but the ratio of both mentioned above is
Calculated relative to the total weight of Ruding material. No noticeable difference was observed even when one resin '&10 was added and the other was added at 60%, or vice versa. However, the pressure stiffness...) force value is 9 times 1li
ka) Owaka 8. If present, add resin in an amount between 15 and 25% of the total dry weight with quartz and observe next time.

Opposition! l stiffness, pressure stiffness, and tensile stiffness all increase unexpectedly as mentioned above, but the increase in tensile stiffness is due to the other two
There were fewer people than people. It is impossible to find a clear answer to the question of why the six types of stiffness increase at different rates.

The average value of the rigidity of the above five types is water glass and silica (silica).
The increase in stiffness was approximately 50% compared to the increase in stiffness obtained when only one or the other of the two resins was added to the composition of ika) and sometimes quartz.

This average value is therefore also slightly lower than the above-mentioned value of 40%.

〔Example〕

Below, some examples of use of the present invention are shown. All of these have been tested and found to be more than satisfactory with respect to the aforementioned advantages.

Example 1 This example relates to the use of the composition as a binder member, particularly when adhesion between two building materials is required in situ. The composition of the composition is as follows.

Sodium water glass, dry type 11 295 parts Quartz powder,
Dry weight 251 parts Silica (fly ash), dry fil 25f! 5 Curing member (sodium hexafluoride) 36 parts This composition has a very good adhesion effect on water glass alone, and also on materials to which conventionally known compositions of water glass cannot be bonded under full heat. The composition cured within 10 minutes after addition of the t0 curing agent. In comparative tests for compositions with curing agents similar to silica (SI) lr: except for silica, curing occurred for at least several hours, and in some cases for 1 hour.
It takes a day or several days.

[Example 2] This example also relates to a composition used as a binder member,
However, this case concerns that between the laminates in architectural laminates. In this case as well, a comparison test with one without the addition of silica (SI) #! I went there, but silica
The compositions containing silica (,1lika) demonstrated a 30% stronger adhesive action compared to those obtained without silica (,1lika). The composition is as follows.

Sodium water glass, dry salt IIT 270 parts Silica (
Fly ash) Dry amount: 11 parts Same curing agent as in Example 1 18 parts This adhesive is, first and foremost, either a conventional water glass-based adhesive that does not adhere at full heat, or a) It was proven that it adhered well to window glass, which is adhesive but not adhesive. This has also been applied to shiny metal surfaces.

Example 6 This test was designed for the production of floor coverings for use in parts of factories where heavy vehicles are operated. The purpose is to provide a long-life sound damping cover. This composition has the following composition.

Sodium water glass 270 parts Quartz powder
300 parts silica
An identical composition was also prepared with 24 parts hardening agent (same as in Example 1) and 18 parts except for the quartz powder. Both sets of parabolites were compared under exactly the same environment and both cured within 8 to 12 minutes after addition of the curing agent.

The waste oil and fat coating did not stick to the floor under full heat, which is considered to be perhaps the most important advantage of this floor covering when used on factory premises.

Both test floor coverings were subjected to artificial strain during the test bank by alternating pushing and vibration of specific strength calculated to correspond to normal strain over a period of 5 years. The surface of the floor covering containing quartz powder remained intact. The surface of the floor covering without quartz powder was found to have small cracks after a period of time corresponding to 4 to 5 years and was not seriously considered. At the same time, the floor covering containing quartz powder is still intact (Example 4), in this case the composition Fi is used for the production of stock for steam generators. The composition is as follows.

Sodium water glass 250 parts Copper grains
750 parts reinforcement material (steel wool)
40 parts Silica (fly ash) 50 parts Curing agent (same as above) 54 parts The heat storage unit was heated to 7JI at the foot of a temperature of 400 degrees C in a steam generator.
I was heated and then sprayed for i seconds in 85
It immediately cools down to a degree C so that the temperature of the fart decreases. Previously, heat storage units with the same composition but without the addition of silica were used for the same purpose.These heat storage units with silica added are heat storage units without silica. It was found that it has an average lifespan of about 8 times that of the main body. The main body of the heat storage device without silica broke into small pieces after a short time, and the small pieces could be called powder depending on the material. [Example 5] In this test, the construction board material was damaged by the addition of acidic cellulose material. □ First, sodium water glass, quartz powder,
A composition containing silica f was prepared separately and then treated with sulfuric acid to pH 1 of Zero 7 IPA wood from Sulphite Pulp Industries, but the material was brought to a low acidity unsuitable for this purpose in a known manner. It's just in case. The pH is thereby adjusted to be equal to 4. In this case, acidic cellulose was found to act as a hardening agent, so conventional hardening agents were not used. The composition was as follows.

Sodium water glass 75 parts by weight Quartz powder
6 parts by weight silica
) 2 '11ils subtotal 4
5 parts cellulose-like substance 55111' 1 part total 1oo*ma composition itself! After construction, the cellulosic material was added and hardening occurred immediately. This is an example 1 to 4
The next day was also a little slow and continued to be a friend.

Before curing continues until the material is hard, it is then put into a mold to make a building board when it is ready to be shaped and shaped into a plastic state.

Thereafter, curing is continued until the plate material is completely cured. Cure proceeds relatively quickly, such that the material changes from a plastic state to a finished solid state in less than 10 minutes until the end point of curing. At this time, the completed construction board can be immediately taken out of the mold.

The finished building board material has higher rigidity than the conventionally known building board material based on water glass and gold.

First of all, however, what is very remarkable is that it has been found to have an elastic restoring force against any shape change, thus preventing defects of this kind that would otherwise easily occur during transportation or installation. Moreover, as a result, the assembly work can be carried out easily and quickly.

Claims (1)

Claims: 1. A process for producing a molding material comprising water glass, preferably sodium water glass, and quartz (SiO_2), possibly also in finely divided form, in which silica (silika) is added before solidification of the water glass. , that is, activated silicon (Si) is added to the water glass in an amount between 3 and 5 percent calculated based on the total dry weight of the materials contained in the molding material, and a hardening agent is also added. A method of manufacturing a molding material. 2. A method according to claim 1, characterized in that cellulose in a finely divided basic state is added to the molding material, said basic state being made of a divalent carbonate. 3. Micronized cellulose in acidic conditions is added in an amount of 5 to 75% by weight of the total dry weight of the molding material, said cellulose preferably consisting of so-called zero fibers of the pulp industry, having a pH between 2 and 6. A method according to claim 1, characterized in that: 4. Process according to claim 6, characterized in that the cellulose material is preferably bark from a pine and contains tannic acid. 5. Claim 3, characterized in that a mixture of water glass, silica, and perhaps also quartz powder, and a cellulose material having a predetermined pH are prepared separately, and then the two materials are mixed. or the method described in paragraph 4. 6. Claims characterized in that an uncured or partially cured plastic emulsion in finely divided form is added to the molding material, and that the curing of the plastic occurs simultaneously with the curing of the molding material. The method according to option 1. 7. characterized in that at least two different plastics, preferably acrylic resins and epoxy resins or carbolic acid resins, are added to the emulsion in an amount between 10 and 30% each based on the total dry weight of the molding material. The method according to claim 6. 8. Preferably a heavy metal such as lead or copper or an alloy containing lead and/or copper is added to the molding material, said metal being in granular form and produced from the molding material for the purpose of a heat accumulator. The method according to any one of the preceding claims, characterized in that: 9. The molding material according to any one of the preceding claims, characterized in that the molding material is made chemically porous by adding tenside thereto in the presence of air before solidification. Method. 10 Plastic is added to the molding material,
10. Process according to claim 9, characterized in that the plastic is of a type that expands under the influence of heat, preferably polystyrene, and the molding material is heated to make the plastic porous.