JPH11254409A - Paper solidified product and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To widen the range of use applications of a paper solidified product, thereby increases the quantity of recycled waste paper by impregnating a paper with an aqueous solution containing an aqueous paper solidified product forming component of alkaline silicate and drying the paper to solidify the permeation solution. SOLUTION: A paper is impregnated with an aqueous solution of alkaline silicate (silicate) and addition products are individually and simultaneously mixed with and dispersed into the aqueous solution. The silicate is a silicate itself or a mixture of the silicate and other components which is called a soluble glass or a liquid soluble glass. The additives to be combined with the soluble glass are a hydrochloric acid, an aluminum phosphate or the like and in addition to the acid and a basic compound, are such as amines or a carbonic acid gas. Theses additives work as a curing agent and a curing promotor for the aqueous solution of the silicate. In order to solidify the paper impregnated with the aqueous solution of the silicate, a mixture of the aqueous solution and the additives or the aqueous solution of the silicate or the additives are individually sprayed or spread over the paper after adjusting the concentration, or the aqueous solution and the paper are mixed simultaneously and the paper is dried to cure the aqueous solution after impregnation. Thus it is possible to obtain the paper solidified product with high heat resistance and superb resistance to a solvent and an oil, and expand the use applications of the paper setting product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solidified paper and a method for producing the same. In recent years, the amount of waste paper waste has tended to increase year by year, but the amount of recycled waste paper is smaller than the amount of waste paper, and a large amount of waste paper has been incinerated.
In particular, it solidifies waste paper, manufactures solidified materials that have both heat resistance and solvent resistance, expands the use of paper, increases the amount of recycled waste paper, and reduces the amount of waste paper that is incinerated. Therefore, the invention is suitable for enhancing the effect of resource saving.

[0002] Here, paper means newspaper, book paper, magazine paper,
It is a concept including document paper, dust paper, wrapping paper, corrugated ball, other paper products and the like, and recycled pulp obtained by defibrating them, as well as natural pulp as a raw material of paper.

[0003]

2. Description of the Related Art As is well known, paper is lightweight, has heat insulating properties, an action of absorbing and relaxing impact (hereinafter simply referred to as "impact relaxation"), a sound absorbing property, and absorbing and retaining liquid. (Hereinafter referred to as “absorbency”).

[0004] In other words, it is known that soft and elastic paper fibers have an effect on impact relaxation, and that a myriad of voids existing between the fibers of the paper have an effect on heat insulation, sound absorption and absorption. Have been.

[0005] Therefore, when the paper is made into a solid product, a light-weight product having both heat insulation, impact relaxation, soundproofing, and absorptivity can be manufactured. It was useful in manufacturing products such as void fillers (packing materials), heat shields, and sound effect materials.

[0006] In the conventional method for producing a solidified paper,
In order to make the paper solid, an organic paper solid forming component (hereinafter, simply referred to as “organic fixing agent”) has been used. That is, a method has been adopted in which an organic fixing agent is dissolved or dispersed in water to form an aqueous solution, and the aqueous solution is permeated into paper and dried.

According to this technique, as the aqueous solution containing the organic fixing agent penetrates into the paper fibers and eventually dries, each of the paper fibers is coated with the organic fixing agent,
The fibers are fixed to each other to form a solid. That is, the production method is such that when the aqueous solution containing the organic fixing agent is completely dried, a solidified paper is formed.

Here, the organic fixing agent includes, but is not limited to, glues such as starch, glue, polyvinyl alcohol, and vinyl acetate. These were used after being converted into an aqueous solution of a hydrosol (in a state of being dispersed in water) and then penetrating into paper.

[0009] More specifically, a solidified paper has been produced as follows. That is, first, the aqueous solution containing the fixing agent is permeated into paper, then the wet paper is formed, and finally, the formed paper is dried to be solidified. It was producing solidified paper.

As a method for infiltrating the aqueous solution into the paper, the aqueous solution is applied to or mixed with a piece of paper in a dry state, or the aqueous solution is mixed with a natural pulp or a regenerated pulp in a wet state. And other techniques were used.

When the wet paper is formed, a mold may be used to form the molded product into a predetermined shape.
In order to stabilize the dimensions of the completed paper solidified product, compression and molding were performed, and further, compression and heating were simultaneously performed to increase the physical strength of the solidified product.

[0012]

The solidified paper produced using the organic fixing agent has the following problems in practical use. (1) The heat stability of the solidified paper produced using an aqueous solution containing an organic fixing agent is affected by the heat resistance inherent in the fixing agent. ) Is also affected by the heat resistance of the binder.

That is, the organic matter is deformed and melted by heat,
Alternatively, when the paper solidified material is immersed in hot oil in a high temperature state, the fixing agent is softened and swelled, and the paper solidified material forming function of the fixing agent is Will be lost. That is, there is a problem that the solidified paper can collapse its shape in high-temperature hot oil.

Then, actually, the conventional paper solidified material is
It could not be used at a location where hot oil heated to 0 ° C. or more spills, or could be used for absorbing hot oil. Therefore, in order to obtain a material for absorbing hot oil, a material having a porous structure of ceramic is used. However, ceramic is disadvantageous in that it is hard, brittle to impact, fragile, and heavy in weight. is there.

(2) Further, the organic fixing agent has a property of being dissolved or swelled by an organic solvent and an oil having a dissolving power (hereinafter, these are simply referred to as “solvents”). Here, when the fixing agent of the paper solidified material is dissolved or swelled, the function of forming the paper solidified material is lost, so that the shape of the paper solidified material is collapsed, and the characteristics as the paper solidified material cannot be exhibited. It will be.

That is, since the conventional solidified paper cannot be applied to a portion in contact with a solvent, there is a problem that it cannot be used for the following applications. That is, when a large amount of a highly flammable solvent is transported, there is a risk of ignition due to vibration or impact during transportation. And as a cause of the ignition,
The wave motion of the solvent caused by vibration or impact (hereinafter referred to as wave motion) can be cited. Specifically, static electricity generated by the wave motion sparks and ignites.

On the other hand, if the solvent is transported in a state of being absorbed in a porous substance, the amplitude of the wave with respect to vibration and impact can be reduced, so that the amount of generated static electricity can be reduced and ignition can be suppressed. Become. Therefore, in order to suppress the occurrence of the above-mentioned ignition phenomenon, it is said that the solidified paper is used as an absorbent material that is lightweight and has excellent impact relaxation properties. It is conceivable to provide for use.

However, for this purpose, the solidified paper must have a solvent-resistant property, so that there is a problem that the solidified paper manufactured by the conventional method cannot be applied to the above-mentioned applications. Was.

In order to solve the above problems (1) and (2), a paint (for example, polyurethane resin, heat-resistant silicon resin, etc.) is applied to a solidified paper produced by a conventional production method and impregnated. A method of forming a coating film and imparting heat resistance and solvent resistance to the solidified product simultaneously or individually.

However, in this method, it is necessary to adjust the viscosity and the concentration of the paint, and further, it is necessary to clean and maintain the coating equipment, which is complicated. However, there is a problem that the manufacturing process becomes complicated.

In the above operation, since an organic volatile solvent is used as a diluent for the paint, it is necessary to wear protective equipment to protect the human body from harmful components of the solvent, or to install a ventilation device. Is required. Further, since the paint containing the organic solvent is easily flammable, there is a risk of fire.

Further, in the method of applying a resin paint to the solidified paper, the paint is absorbed by the solidified paper, the voids in the solidified paper are filled with the paint, and the surface of the solidified paper is sealed with the paint. The phenomenon that it is done occurs.

In this case, the heat insulating property, sound absorbing property, liquid absorbing property, shock absorbing property, and the like, which are inherent properties of the solidified paper, are impaired. That is, by applying the coating material, the inherent properties of the solidified paper are lost, so that the use of the solidified paper is limited, and the practical range is narrowed.

The properties of the paint that coats the surface of the solidified paper are affected by the properties of the resin that constitutes the paint.
It is well known that the type of resin differs for each type.

Therefore, the stability of the paint to heat and solvents is not uniform, so that it is not necessary to select an appropriate resin according to the use conditions such as the type of the solvent or the temperature of the oil, and to use different resins. There was annoyance that it should not be.
Nevertheless, coatings could not cope with solvents having still high solubility or even higher temperatures.

The present invention has been made in view of the above-mentioned problems, and is intended to realize a solidified paper having high heat resistance and solvent resistance. Instead of using an organic fixing agent which has been conventionally used, an inorganic fixing agent is used. Paper solidified material forming component (hereinafter simply referred to as "inorganic solidifying agent")
(Hereinafter referred to as "penetration") into paper to make it possible to realize a heat- and solvent-resistant solidified paper, thereby solving the above problems.

As a result, the use of the solidified paper is expanded,
It is an object of the present invention to provide a paper solidified material capable of increasing the amount of waste paper used, thereby increasing the resource saving effect, and a method for producing the same.

[0028]

The technical problem of the present invention is solved by the following means. A first aspect of the present invention is a paper solidified product obtained by infiltrating an aqueous solution containing an aqueous paper solidified material forming component composed of an alkali silicate into paper, and then drying and curing the paper.

As described above, the aqueous solution containing an aqueous paper solidified material forming component composed of an alkali silicate is penetrated into the paper,
Since the solidified paper obtained by drying and curing is solidified using an inorganic paper solidifying agent such as an alkali silicate, the solidified paper has heat resistance, solvent resistance, and oil resistance.
This can contribute to the expansion of the use of solidified paper.

The second aspect of the present invention is to infiltrate the paper with an aqueous solution containing an aqueous paper solidified material-forming component, and further dry and harden the aqueous solution.
A method for producing a solidified paper having heat resistance, solvent resistance, oil resistance and the like, wherein an alkali silicate is used as a solidified paper forming component of the aqueous solution. Is the way.

As described above, according to the production method of solidifying the aqueous solution using the alkali silicate as a paper solidified material-forming component, the paper material can be solidified even at room temperature. In addition, since it is a method of forming silicic acid in paper and using the silicic acid as a solidifying agent to form a solidified paper, it is easy to stabilize a solidified paper that has heat resistance, solvent resistance, oil resistance, etc. Can be manufactured. Various additives can be used as a curing agent or a curing accelerator for the aqueous silicate solution, and carbon dioxide in the atmosphere can also be used.

A third aspect of the present invention relates to an aqueous paper solidified product forming aqueous solution containing an alkali silicate as a paper solidified product forming component for solidifying paper, wherein the aqueous paper solidified product forming solution comprises an alkali silicate It is an aqueous solution for forming a solidified paper, which is configured to function with an aqueous salt solution and an additive.

As described above, since the aqueous solution for forming an aqueous paper solidified product is configured to function with the aqueous solution of the alkali silicate and the additive, the aqueous solution containing the alkali silicate is penetrated into the paper. When forming and manufacturing a solidified paper having both heat resistance and solvent resistance, the alkali silicate and the additive are allowed to act individually, or the alkali silicate and the additive are individually and simultaneously In combination, the aqueous solution can penetrate the paper.

By selecting the type of additive and blending it, it is possible to increase the rate of generation of crystalline silicic acid from the silicic acid aqueous solution. It can also be used as an anti-condensation or sound-proof paint.

[0035]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, an embodiment will be described in which the solidified paper having both heat resistance and solvent resistance according to the present invention and a method for producing the same are practically embodied. In addition, in this specification, a compounding unit is a weight unit unless there is particular notice.

(1) The inorganic solidifying agent used in the production method of the present invention is an alkali silicate (hereinafter, simply referred to as “silicate”), and an aqueous silicate solution is used to form a solidified paper. use. And silicate is an inorganic substance.

This aqueous solution is used by permeating the aqueous solution into paper. The additives are individually and simultaneously mixed and dispersed in an aqueous solution.

(2) In the present invention, the silicate is a simple substance or a mixture of the silicate represented by the general formula M2nSiO2, and is usually called water glass or liquid water glass. In the above general formula, M is Na, K, Li
Such as sodium silicate,
They are called potassium silicate and lithium silicate. And, in the present invention, powdery sodium silicate (anhydride)
Can be used similarly to liquid water glass.

Here, n is an integer. The value of n is preferably about 1 to 3, but is not particularly limited.

These may be in a range that does not affect the water solubility and permeability and the properties of the solidified paper when actually used.

The aqueous solution has a silicate concentration of usually 50 to 990 g / L, preferably 100 to 1000 g / L.
L is used.

(3) Additives used in combination with the above aqueous solution (silicate aqueous solution) include hydrochloric acid, aluminum phosphate and the like.
In addition to acids and basic compounds, there are amines and carbon dioxide.

These additives act as a curing agent and a curing accelerator for the aqueous silicate solution (water glass).

In the classification of the hardening agent and the hardening accelerator in the aqueous silicate solution, a substance which rapidly releases silicic acid from the aqueous solution when mixed with the aqueous silicate solution is conventionally called a hardening agent. .

However, to be precise, the hardening accelerator belongs to the type of hardening agent because it has an action of releasing silicate from the aqueous silicate solution (therefore, both the hardening accelerator and the hardening agent are collectively referred to as a hardening accelerator). In the following, these are simply referred to as “additives”).

Since carbon dioxide present in the atmosphere also promotes the hardening of the silicate, carbon dioxide is also an additive here.

The mechanism of the hardening action or the hardening promoting action is based on the following theory, which is described in the literature (Translator of "water glass" by Herman Meyer:
Susumu Okuda, published by Corona).

That is, the aqueous silicate solution (water glass) forms free silicic acid or various compounds containing free silicic acid by a drying action (action of carbon dioxide gas in the atmosphere) or a curing action of an additive. Free silicic acid polymerizes to form orthosilicic acid in a narrow sense. Then, these silicic acids are hardly soluble in water and are chemically stable to erodible chemicals such as hydrochloric acid, sulfuric acid, and nitric acid.

The following is described in the above-mentioned literature regarding the properties of silicates against heat. That is, when the silicate aqueous solution is heated to evaporate and concentrate water, a gel-like film is formed.

When the aqueous solution is rapidly heated to about 500 ° C., the film becomes a foam containing fine air bubbles. Therefore, there is a method for producing a heat insulating material from an aqueous silicate solution. Also, the melting point of crystalline silicate is shown below, and silicate is a non-combustible substance.

That is, orthosilicate soda (Na4Si0
4); 1,083 ° C, sodium metasilicate (Na2SiO
3); 1,088 ° C., potassium metasilicate (K2SiO3);
976 ° C, lithium orthosilicate (Li4SiO4);
1,255 ° C, lithium metasilicate ((Li2SiO
3); 1,201 ° C. and the like are described.

The aqueous silicate solution used in the above method is used as a solution in which silicates are individually or combined, and the solution may further contain a curing agent and a curing accelerator in an optional combination as additives. Is added.

The above-mentioned additive does not hinder the operation of producing the solidified product, such as rapidly increasing the viscosity or gelling of the silicate aqueous solution, or the formed paper solidified product. What is necessary is just to have the structure which does not disturb the property.

Specifically, an additive is used in the following procedure to solidify the paper impregnated with the aqueous silicate solution. (1) Air is mixed with an aqueous silicate solution so that the carbon dioxide component contained in the air effectively acts as an additive of the aqueous silicate solution, and then the aqueous solution is permeated into paper, or First, a method in which an aqueous silicate solution is permeated into paper, and then the carbon dioxide gas in the air is allowed to act on the paper. (2) When an additive other than carbon dioxide is used in combination, there are the following two methods. (a) A method of infiltrating a paper with an adjustment liquid prepared by mixing an aqueous silicate solution and an additive in advance. (b) A method in which one of the additive and the aqueous silicate solution is made to penetrate the paper, and then the other is made to penetrate to make the paper interact.

Further, the following method is used in order to infiltrate the paper with a silicate aqueous solution or an additive. In other words, an aqueous solution in which an additive is dissolved or dispersed in water is prepared, and the concentration of the silicate aqueous solution is adjusted, and then these solutions are individually sprayed or sprayed on paper to penetrate the paper. There is a method of simultaneously mixing the individual aqueous solutions and the paper, and the like, and any method may be used as long as the above-mentioned solution does not inhibit the effect of the solution permeating the paper.

The method of forming and drying / curing the paper that has absorbed the silicate aqueous solution to which the additive is disposed may be any method that does not cause an abnormality in the properties of the formed paper solidified material, and is not limited. Absent.

[Experiments] The following various experiments were conducted in order to examine various properties of the solidified paper formed by permeating the paper by using a silicate aqueous solution and an additive in combination with the solvent.

Experiment 1: Solvent resistance In order to confirm the situation where the solidified paper was affected by the solvent and the solidification state was unstable, the solidified paper was immersed in a solvent according to the following procedure. The time required until a change in the solidification state appeared was measured, and the solvent resistance was compared.

[Explanation of Experimental Procedure] A solidified paper having a size of 3.times.3.times.3 cm was used as a test sample, and was immersed in a solvent. The sample was placed on the upper surface of the sample, and the shape of the square of the sample was deformed or collapsed by the weight of the weight, and the time required for the shape to change was measured. Then, the solvent resistance of the test sample was measured based on the evaluation criteria that the test sample whose shape did not change even after being immersed for a long time had excellent solvent resistance.

[0060]

[Table 1]

The test pieces were adjusted to the compositions shown in Table 1 and then poured into a mold to be molded. Then, after leaving it to dry at room temperature for 4 weeks, it was further dried for 24 hours in a dryer kept at 100 ° C. for adjustment.

Further, in order to compare the performance of the specimen with respect to the solvent, a comparative specimen (hereinafter simply referred to as “comparative body”) prepared in the same manner as the specimen was prepared, and the test under the same conditions as the specimen was performed. Was served. Then, in order to compare the specimen with the solidified paper formed by the same method as the conventional method, the comparative body was a solidified paper using an organic fixing agent. The organic fixing agent was mixed with water according to a conventional procedure so that the solid content was 35% or more, and then absorbed on paper.
Table 2 shows the composition of the comparative body.

[0063]

[Table 2]

Table 3 shows the measurement results in this experiment.

[Table 3]

As a result of Experiment 1, the comparative substance formed with the organic fixing agent was used in four kinds of solvents such as alcohols, aromatics, esters, and ketones. When immersed in an oil skydolol (containing an ethylene glycol / monoether-based component in the composition) and subjected to the above-mentioned load every hour, all of the comparative materials undergo shape collapse within 3 hours. Was.

From this, it was found that the performance of the organic fixing agent for maintaining the shape of the solidified paper was destabilized by the action of the above-mentioned solvent, fuel and lubricating oil. That is, the solidified paper obtained by the conventional production method did not show stability against the solvent.

On the other hand, in a test performed on the test piece using the inorganic solidifying agent by the same method, no significant change appeared even when a load was applied to the test piece every hour. Then, a test in which the above-mentioned load was applied every 24 hours was performed, and it was observed that the shape of the test piece collapsed, but no change in the shape appeared. That is, it has been found that the performance of maintaining the shape of the paper solidified product by the solvent, the fuel and the lubricating oil is not made unstable in the test sample.

Further, when the amount of silicate is increased in the aqueous silicate solution and the concentration thereof is increased,
The shape of the specimen, the solvent, fuel and lubricating oil,
It was more stable. From this, it was found that the solvent resistance of the solidified paper improved in proportion to the silicate concentration.

Experiment 2: Heat resistance test A method of immersing a test sample and a comparative sample prepared in the same manner as in Experiment 1 in hot oil and measuring the temperature of the oil when its shape changes. A test was conducted to compare the heat resistance of the test specimen and the comparative specimen.

[Test Method] A test sample and a comparative sample having the same dimensions as those in Experiment 1 were tested according to the following procedure, and the heat resistance of both samples was compared.

First, the test sample and the comparative sample were placed in respective beakers, and then 300 cc of motor oil (SEA20-50) was poured from above, and the mixture was left for 1 hour, and the test sample and the comparative sample were added with the above oil. After absorption, the oil was heated by heating the oil with a gas burner flame onto the beaker.

Then, the temperature at which the shape of the oil changed was measured, and the heat resistance of the sample was compared with the temperature of the comparative sample by comparing the temperatures of the sample and the comparative sample. Table 4 shows the results.
And Table 5 below.

[0073]

[Table 4]

[0074]

[Table 5]

From the results of Experiment 2, the shape of the comparative body was
Before the temperature of the tar oil reached 200 ° C., it was burnt with fuming, shattered and collapsed. However, in the test sample, although the smoke phenomenon occurred like the comparative sample,
When the temperature reached 250 ° C., the shape was still stable. The shape did not change even after the specimen was taken out with tweezers. From this, it was found that the test specimen had better heat resistance than the comparative specimen.

Experiment 3: Boiling test A sample of a paper solidified product obtained by solidifying paper using a silicate aqueous solution as a paper solidifying component and a comparative example of a paper solidified product obtained by a conventional manufacturing method were prepared. In order to compare the stability of boiling water in hot water, these were immersed in boiling water, the temperature of the water was kept at 100 ° C, and the time required for each shape to change was measured. (Boiling resistance).

[Test Method] A test sample and a comparative sample prepared in the same manner as in Experiment 1 were tested by the following procedure, and the boiling water resistance of each test sample and the comparative sample was compared.

First, 500 cc of pure water placed in a beaker was heated to boil the water, and then the test specimen and the comparative specimen were individually immersed in boiling water to keep the boiling state. Then, the time required for each shape to be changed with hot water is measured, and the evaluation method is such that the longer the time required for the shape change is, the better the boiling water resistance is. Boiling resistance of the bodies was compared.

The results are shown in Tables 6 and 7.

[Table 6]

[0080]

[Table 7]

From the results of Experiment 3, the shape of the comparative material was collapsed immediately after being immersed in boiling water so that the shape could not be confirmed. However, the shape of the specimen was stable even when heating was continued until the water in the beaker was completely evaporated. From this, it was found that the specimen had better boiling water resistance than the comparative specimen.

Therefore, in order to confirm the relationship between the silicate concentration and the boiling water resistance, a silicate aqueous solution having a reduced silicate concentration was prepared, and the boiling water resistance of the specimen prepared using this aqueous solution was adjusted. Was measured in the same manner as in Experiment 3.

Table 8 shows the adjusted compositions of the test pieces, and Table 9 shows the results.

[Table 8]

[0084]

[Table 9]

From the results of the additional test, it was found that the boiling water resistance was improved in proportion to the silicate concentration.

Experiment 4: Water Absorption Test The water absorption of the solidified paper containing silicate as a component for forming the solidified paper is related to the lightness, heat insulation, impact relaxation, sound insulation and the like inherent to the solidified paper. In particular, the water absorption was calculated by the following method in order to confirm the fact that the performance of absorbing the solution of the solidified paper was related.

[Test Method] The dimensions of the specimens adjusted in the same manner as in Experiment 1 were set to 5 × 5 × 3 cm, and the water absorption of each specimen was measured in the following procedure.

First, the specimen was placed in a constant temperature dryer at 100 ° C. and dried for 24 hours, and then the weight (W) of the specimen was measured.
Was measured. Next, the sample was immersed in pure water for 15 minutes and then taken out. The surface was quickly wiped with a wet cloth, the weight (T) was measured, and the water absorption (K) was obtained from the following formula.

For comparison, a comparative sample having the same composition as that used in Experiment 1 was measured in the same manner as described above.

K (%) = [(T−W) / W] × 100 The results of the experiment are shown in Table 10.

[Table 10]

Experiment 5: Measurement test of porosity The porosity of the solidified paper containing silicate as a component for forming the solidified paper was determined by the lightness, heat insulation, impact relaxation,
Because it is related to soundproofing and the ability to absorb solution, etc.
To confirm, the porosity was calculated by the following method.

[Test Method] A specimen having the same composition as that used in Experiment 1 was prepared and dried by the same method as in Experiment 1, and then the porosity of each specimen was measured by the following procedure. did.

First, the weight (W) of the specimen was measured, and the dimensions of the specimen were accurately measured using calipers to obtain the volume (L).
Then, the specimen is immersed in pure water for 60 minutes, taken out, and its surface is quickly wiped with a wet cloth. Then, the weight (T) is measured, and the porosity is calculated from the following formula. V) was determined.

For comparison, a comparative sample having the same composition as that used in Experiment 1 was measured in the same manner.

V (%) = [(T−W) / L] × 100 The results of the experiment are shown in Table 11.

[Table 11]

From the results of Experiments 4 and 5, it was found that the water absorption and the porosity of the test sample tended to increase in inverse proportion to the silicate concentration in the aqueous silicate solution.

When the measured values of the water absorption and the porosity were compared between the test sample and the comparative sample, all the values were close to each other. This means that by adjusting the silicate content of the specimen, it is possible to adjust the numerical values of the water absorption and the porosity of the specimen to match the numerical values of the water absorption and the porosity of the comparative specimen. It indicates that there is.

Experiment 6: Compressive strength measurement test In order to confirm the mechanical strength of a paper solidified material specimen containing silicate as a paper solidified material-forming component, the compressive strength was measured by the following method.

[Test Method] A specimen having the same composition as that used in Experiment 1 was prepared, dried by the same method as in Experiment 1, then placed in a constant temperature drier at 100 ° C. and dried for 24 hours. The compressive strength of the specimen was measured according to the following procedure.

First, the dimensions of the square of the specimen are measured, and the area of the top surface (S ₁ ) and the area of the bottom surface (S ₂ ) are calculated.
Next, the sample was set on an Amsler compression tester, and the pressure was gradually applied from the upper surface of the sample, and the pressure (P) at the time when the sample was broken by the pressure was measured. (F) was measured.

For comparison, a comparative sample having the same composition as that used in Experiment 1 was measured by the same method.

F (Kg / cm ² ) = P / S S = (S ₁ + S ₂ ) / 2

Table 12 shows the results of the experiment.

[Table 12]

From the results of Experiment 6, the compressive strength of the test piece was
It has been found that the amount tends to increase in proportion to the amount of the silicate.

Experiment 7: Flexural strength test of compression-molded paper solidified paper A mixture prepared by simultaneously mixing an aqueous silicate solution, paper, and additives was placed in a mold, compressed and molded into paper. The bending strength of the solidified product was measured by the following method.

[Test Method] The same composition as the specimen used in Experiment 1 was prepared by adjusting only the water content to obtain the composition shown in Table 13, and this was used as a mold for a hydraulic porcelain tile compression molding machine. frame (width 5.5cm, length 15cm, thickness 1.5 cm) after putting on, 300 Kg / cm ² and, of 500 Kg / cm ² 2
Each type of pressure was applied to form two types of molded articles, which were air-dried for 4 weeks.
The sample was placed in a constant temperature drier maintained at 00 ° C. and dried for 24 hours to obtain a specimen. And the bending strength of the specimen was measured by the following procedures.

[0107]

[Table 13]

First, the width (L2) and thickness (H) of the specimen
Was measured, and then applied to an Amsler-type strength tester to apply pressure to the specimen as described below, and the bending strength of the specimen was measured from the following equation.

That is, an iron plate having a blade with a thickness of 1 cm was attached to the pressing shaft of the testing machine so as to form a pressing plate, and the pressure receiving base of the testing machine was 5 cm on a side and 10 cm in length. Triangular prism 2
The books were placed in parallel at intervals of 10 cm, and when the specimen was placed thereon, the triangular prism became a parallel fulcrum that supported two points of the specimen. Parallel to and at the midpoint of each fulcrum, and set it in contact with the specimen, lower the push plate of the tester, measure the pressure (F1) when the specimen breaks, and use the following formula , Thickness 1c
The bending strength (B) of the m specimen was calculated.

For comparison, a comparative sample having the composition shown in Table 14 was measured in the same manner.

[0111]

[Table 14]

[0112] Further, two specimens, ie, a test specimen and a comparative specimen prepared by using the same composition and the same molding method as in Experiment 1,
It was measured in the same manner as above.

B (Kg / cm ² ) = F ₁ / L ₂ × 1 × H The results of the experiment are shown in Table 15.

[Table 15]

From the results of Experiment 7, the bending strength of the specimen was
It has been found that the bending strength of the test piece is proportionally improved when the silicate content in the silicate aqueous solution is increased in proportion to the molding pressure, and when the silicate content in the silicate aqueous solution is increased.

Similarly, it was found that the flexural strength of the comparative body improved in proportion to the molding pressure.

[0116]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Various embodiments of the present invention will be described below.

Example 1 In order to investigate the effect of the solidified paper obtained by solidifying the paper by the production method of the present invention on the liquid level motion, a cubic mold having a length of 20 cm, a width of 20 cm and a depth of 15 cm was first prepared. A prepared iron container was prepared.

[0118]

[Table 16] A specimen having the composition shown in Table 16 was prepared in the same manner as in Experiment 1, and the solidified product was 20 cm long, 20 cm wide and 1 cm high.
The sample was processed into 3 cm, and was pushed into the container just as described above so as to fit into the container, so that the top of the specimen was adjusted to a position at a depth of 2 cm of the container.

[0119]

[Table 17] Next, the solvent shown in Table 17 was poured into the sample at a depth of 2 cm to absorb the sample, and the sample was saturated, and then covered with a transparent acrylic plate (21 cm × 21 cm × 0.2 cm). ,
It was fixed with adhesive tape. Further, for comparison, only the above-mentioned solvent was poured into a container having the same shape so that the liquid level was at a position of 2 cm from the upper end of the container, and then covered with a transparent acrylic plate having the same dimensions as above. And fixed with adhesive tape.

In order to observe and measure the behavior of the solvent in each container with respect to the shock, the shock generated under the same conditions is applied to both the container in which the test sample and the solvent are sealed and the container in which only the solvent is sealed. Then, the following method was used. That is, in order to prevent bubbles mixed in the solvent from affecting the test results, pour the solvent into both containers,
The mixture was allowed to stand for a minute and degassed.

The following pendulum device was installed as a device for giving an impact to the container, and the iron ball of the pendulum was made to collide with the container. That is, a fulcrum is provided just above the container so that the iron ball of the pendulum can hit the center of the side surface of the container, and a string is tied to the fulcrum.
An iron ball weighing 38 g was fixed.

Then, when the iron ball kept at a fixed position is pendulum-moved from the container, the iron ball hits the container. Then
The solvent in the container exhibits the phenomenon of generating waves upon impact (hereinafter, referred to as
This phenomenon is called "wave." If the vibrations increase, the solvent will scatter from the container and contaminate the transparent acrylic plate. In addition, the magnitude of the wave is slightly affected by the kinetic energy of the iron ball.

Since the kinetic energy of the iron ball is proportional to the weight of the iron ball and the distance between the iron ball and the container, the solvent in the container scatters and the container when the transparent acrylic plate is contaminated. By measuring the distance from the iron ball, it can be confirmed that the specimen in the container has an effect of suppressing the generation of the wave. That is, the behavior of the test piece with respect to the solvent was examined by an evaluation method in which the longer the measured distance, the more difficult it was for a wave to occur.

The compositions shown in Table 16 were obtained by performing the same test after comparing and comparing the differences with the conventional method to confirm them. Tables 18 and 19 show the measurement results.

[0125]

[Table 18]

[0126]

[Table 19]

The details of the compositions used in the examples are as follows. (1) Aqueous sodium silicate solution: an aqueous solution with a molar ratio of 3 and a concentration of 70% (2) Aqueous potassium silicate solution: an aqueous solution with a molar ratio of 2 and a concentration of 70% (3) Lithium silicate aqueous solution: a molar ratio of 3.5 and a concentration of 70 %
(4) Aluminum tripolyphosphate: powder with a purity of 80% (5) Zinc oxide: a dispersion solution in water with a concentration of 48% (6) Powdered sodium silicate: a molar ratio of 3, J-type sodium silicate 3 Powder

Further, in order to compare the difference from the conventional solidified paper, a comparative body having the composition shown in Table 14 was prepared by the same method as in Experiment 1, and compared by the same method. Table 20 shows the measurement results.

[0129]

[Table 20]

From the results of Example 1, it can be seen that the solidified paper solidified by the method of the present invention makes it difficult for the solvent to oscillate when subjected to an impact applied to the solvent, thereby maintaining the liquid surface in a stable state. do. In other words, the solidified paper can be used to suppress the wave of a liquid such as a solvent against the impact during transportation,
It is valid.

As for the comparative samples, all the comparative samples were in a non-solidified state while the solvent was allowed to absorb into the comparative samples for testing and then allowed to stand for 60 minutes for defoaming. . Therefore, it has become impossible to measure the behavior with respect to the wave as the solidified material. In other words, it has become clear that the solidified paper obtained by the conventional method cannot be used as a solidified product for the purpose of suppressing the vibration of the solvent, and has not been practically used in the past.

[Example 2] An underground room (3.0 m wide, 4.8 m deep, 1 m high) in which dew forms on the concrete ceiling and the wall surface, and especially when the humidity is high such as during rainfall, water accumulates on the floor. wall of .9m) 23.16m ² and, ceiling 14.4m
² , a coating of the solidified paper obtained by solidifying the paper by the method of the present invention is applied, and in order to prevent dew condensation using the heat insulating property of the paper, a layer of the solidified paper is formed on site in the following manner. The construction was carried out to form

[0133]

[Table 21]

[0134]

[Table 22]

First, a composition shown in Table 21 (hereinafter, referred to as A) and a solution composed of the composition shown in Table 22 (hereinafter, referred to as B) were prepared. Next, on the day of construction, A and B are mixed and kneaded at the construction site to form a mixture, and immediately using an air spray type spraying device called a stucco gun on the concrete body of the ceiling and wall. 6.0 kg per unit area so that the average thickness is 5.0 mm.
/ M ² was applied. The construction was performed after the concrete base had been dried.

Therefore, when a mixture obtained by mixing A and B is applied to a concrete in a dry state, a large amount of an aqueous silicate solution contained in the mixture is prevented from being absorbed by the concrete. Then, a water-retaining powder (product of Arakawa Chemical Industry Co., Ltd.) containing a polyacrylate was added to and mixed with the mixture. Then, in order to make the addition amount not affect the effect of preventing dew condensation, the addition amount was set to 0.3% with respect to the total amount of the silicate aqueous solution amount and the water amount in the mixture.

The details of the compositions of A and B prepared for use in the examples are as follows.

(1) Powdered sodium silicate: molar ratio 3, powdered sodium silicate No. 3 (manufactured by Nippon Chemical Industry Co., Ltd.) (2) Aluminum tripolyphosphate powder: purity 80% (3) Waste paper (newspaper): defibration Processed product, water content 65%

The aluminum tripolyphosphate powder is used for rapidly curing an aqueous solution of silicate and for making the cured product water-resistant.

Therefore, after the dew condensation is prevented on the ceiling and the wall surface of the concrete by the above method, on the second and ninth months,
In order to check the construction surface, the following tests were tried, but the results were satisfactory, and the purpose of the paper solidified product by the method of the present invention was achieved.

That is, in the basement, the concrete base not subjected to the dew condensation prevention and the above-mentioned coating were subjected to a tester for electric resistance measurement.
When the electrical resistance of water was measured by contacting the ends of the + and-side conductive wires, the measured value was obtained on the concrete base, but the measured value was shown at the place coated with solidified paper. Did not.

[Example 3] When waste produced after subjecting the solidified paper obtained by the method of the present invention to use for absorbing solvents and fats and oils was incinerated, the solvent absorbed in the solidified paper was removed. To examine the effect on fats and oils,
0. Part, the aqueous solution of sodium silicate 50. Part, aluminum tripolyphosphate powder7. Part, and tap water 50. The specimen composed of the parts was adjusted in the same manner as in Experiment 1, and a comparative body adjusted in the same manner as in Example 1 was prepared.
The two substances were burned by absorbing the following substances, and the state of the combustion was compared by the following method.

Method for comparing the state of combustion: In order to observe whether or not each of the absorber and the substance to be absorbed burns without interruption, the specimen and the comparator which have absorbed the solvent and the fat and oil are burned. We used the best method. First, the test sample and the comparative sample were processed into a cube having a size of 1 × 1 × 10 cm, and then immersed in a solvent / oil or fat having a composition shown in Table 21 until it was saturated.

Next, two iron holders each having an insertion opening of 2 cm in depth were attached to a metal column, and the respective end portions of the specimen and the comparative body were inserted into the holders. It is possible to fix it while keeping it.
Then, one end of each of the specimen and the comparative body having absorbed the same substance was fixed, and the state of combustion was observed and compared by a method of simultaneously igniting them.

The substances individually absorbed in both the test sample and the comparative sample in the examples are as follows.

(1) Methanol alcohol (2) Motor oil: SEA40

[0147] Then, the specimen and the comparative body were wrapped in flame within a short time after ignition. Then, in the course of combustion, in all of the comparative bodies, a phenomenon in which the vicinity of the center of the solidified body was broken occurred, and a part of the comparative body in a burning state fell on an iron plate laid on the floor. The fallen objects, both those absorbing volatile methanol alcohol and those absorbing non-volatile motor oil, spontaneously extinguished after burning for a while on the iron plate Each residue was generated.

Therefore, the above two types of residues were exposed to the flame of a gas burner and ignition was attempted again. The residues generated by absorbing methanol alcohol were brittle.
It could not be ignited because it was shattered and scattered by the flame. However, the residue generated by absorbing the motor oil can be seen in the unburned motor oil,
When burned by the burner, it started burning again, producing black smoke.

However, this combustion is interrupted as soon as the burner flame is moved away, so that it was necessary to keep burning the burner flame to the residue in order to continue the combustion state. The flame burned out and the comparator burned out before the motor oil burned out. As a result, a large amount of unburned motor oil remained on the iron plate.

[0150] In order to examine the tendency of the comparative body to burn oil, edible olive oil, spindle oil, and fuel heavy oil were prepared, and the comparative bodies absorbed with the respective oils were burned in the same manner. The residue was exposed to a burner flame, and showed the same combustion state as above. From this, it was found that the comparative body was not suitable for a medium for burning fats and oils.

Further, when the state of combustion of the test specimen was observed, the combustion was continued while all the test specimens were fixed to the holder. Therefore, after the combustion of the specimen was extinguished, the flame of the gas burner was applied to both the combustion residue of the specimen absorbing alcohol and the combustion residue of absorbing the motor oil. , These residues were only glowed red.

That is, no sign indicating that alcohol or motor oil remained in the unburned state in the combustion residue of the test specimen could not be confirmed. Furthermore, even if the combustion residue of the specimen is cooled after being heated to red by applying a burner flame, it remains in a solidified state at room temperature and does not burn out and disappear like the comparative example. Was.

Therefore, in order to compare the phenomenon of burning the combustion residue of the specimen with the burner flame after the oil was absorbed into the combustion residue of the specimen and burning the combustion residue of the comparative body, edible olive oil, spindle Oil and heavy oil for fuel were prepared, and the fats and oils were respectively absorbed into the combustion residue of the specimen, and then the gas burner flame was applied.

[0154] Then, these residues were brought into a burning state again, and the burning was ended and the fire was extinguished. A gas burner flame was applied to confirm that no oil was left in the residue.However, it was not possible to confirm smoke or a flame indicating that oils and fats were burned just because the residue was red-heated. could not.

[0155] Even if the combustion residue of the test piece is cooled after being red-heated by irradiating a burner flame, it remains in a solid state at normal temperature and burns out like a comparative example. It did not disappear. From this, it was found that the specimen was suitable for an oil combustion medium and could be used in the field of oil and fat combustion.

[Example 4] In Example 3, in the method of the present invention, an aqueous silicate solution and an additive were allowed to act on paper to form a solidified paper in advance, and the oil was converted into a solidified paper. It was proposed that the solidified paper of this method could be used as a medium for burning oil by absorbing it.

However, in the present method, when the aqueous silicate solution and the additive are allowed to act on the paper, a liquid oil can be simultaneously blended to form an oil-containing paper solidified product. The following oil-containing paper solidified material forming method was implemented in order to provide the above-mentioned applications.

First, 25.0 parts of waste paper (newly cut newspaper), 5.0 parts of the aluminum tripolyphosphate (powder), and 25.0 parts of tap water were mixed to prepare a wet paper. Next, 25.0 parts of the waste oil (motor oil) extracted from the engine of the automobile was added to the No. 3 silicate soot.
An aqueous solution of oil dispersion was prepared by mixing 25.0 parts of an aqueous solution.

Then, after mixing the aqueous solution and the wet paper, the mixture is placed in a cylindrical mold (inner diameter: 3.0 cm, length: 20.0 cm), squeezed with a stick and left for 2 days, The paper was taken out of the frame, and in order to remove the incorporated water, a solidified paper containing oil was formed by a procedure of air drying.

The oil-containing paper solidified product was a solid product having a hardness that would not hinder handling when it was removed from the mold, and the oil did not separate and flow out of the paper solidified product. .

Therefore, the oil-containing paper solidified product was prepared in the same manner as in Example 3 above.
After burning in the same manner as above, the burning state continues until the waste oil in the solidified paper burns out, and the burning residue generated at that time is red-heated by the burner flame, and then cooled, at room temperature. The solidified state was maintained, and it did not burn out and disappear.

From the above, in the present production method, the oil-containing paper solidified material prepared by simultaneously using oil can solidify liquid oil to make it easy to carry, and furthermore, Was found to be suitable as a combustion medium for
It can be used in the field of solidifying fats and oils and burning fats and oils.

Example 5 A basement (3.0 m in width, 4.8 m in depth, and 1 m in height) in which dew forms on the ceiling and wall of concrete and water is accumulated on the floor particularly when the humidity is high such as during rainfall. wall of .9m) 23.16m ² and, ceiling 14.4m
² , a coating of the solidified paper obtained by solidifying the paper by the method of the present invention is applied, and in order to prevent dew condensation using the heat insulating property of the paper, a layer of the solidified paper is formed on site in the following manner. The construction was carried out to form

First, a composition (hereinafter, referred to as A) shown in Table 21 and a solution (hereinafter, referred to as B) having the composition shown in Table 22 were prepared. Next, on the day of construction, A and B are mixed and kneaded at the construction site to form a mixture. Immediately, using an air spray type spraying device called a stucco gun, a thickness is applied to the concrete base material on the ceiling and wall surfaces. 6.0 kg per unit area so that the average is 5.0 mm
/ M ² was applied. The construction was performed after the concrete base had been dried.

In order to prevent a large amount of the silicate aqueous solution contained in the mixture from being absorbed by the concrete when the mixture obtained by mixing A and B is applied to the concrete in a dry state. Then, a water-retaining powder (product of Arakawa Chemical Industry Co., Ltd.) containing a polyacrylate was added to and mixed with the mixture.

Then, in order that the amount of addition does not affect the effect of preventing dew condensation, the addition amount of 0.3% with respect to the total amount of the aqueous solution of silicate and the amount of water in the mixture is used. And

The details of the compositions A and B prepared for use in the examples are as follows. (1) Powdered sodium silicate: molar ratio 3, powdered sodium silicate No. 3 (manufactured by Nippon Chemical Industry Co., Ltd.) (2) Aluminum tripolyphosphate powder: 80% purity (3) Waste paper (newspaper): defibrated product, Water content 65%

The aluminum tripolyphosphate powder is used to quickly cure an aqueous silicate solution and to make the cured product water-resistant.

Then, after the dew condensation was prevented on the ceiling and the wall surface of the concrete by the above-mentioned method, the second and ninth months,
In order to check the construction surface, the following tests were tried, but the results were satisfactory, and the purpose of the solidified paper by the manufacturing method of the present invention was achieved.

That is, a tester for measuring electric resistance was applied to a concrete base not covered with dew condensation in the basement and the above-mentioned coating.
When the electrical resistance of water was measured by contacting the ends of the + and-side lead wires, it could be measured on the concrete base, but did not show the measured value at the place coated with the solidified paper .

At this time, a square metal plate having a side of 5 cm is attached to each end of the lead wire of the tester, and the metal plate is pressed against the measuring point at an interval of 5 cm. The electrical resistance was measured. When measuring,
The gauge pointer of the tester's continuity meter touched greatly on the concrete ground where condensation had occurred, indicating the presence of conductive water.However, the gauge pointer should be touched where the solidified paper of this manufacturing method was coated. And showed no presence of water.

Example 6 The above-mentioned powdered sodium silicate 4
0. Part of newspaper 100. Part and water Parts of the mixture, and further, the aluminum tripolyphosphate powder 2
2. Part was added and mixed, and the adjusted paper was packed into a mold of a porcelain tile base molding machine (hydraulic press), compressed by applying a pressure of 600 kg, and tiles of 15 × 15 × 1.6 cm size were applied. And 12 were left to dry at room temperature for 7 days. The remaining 12 were placed in a drier and heated to 60 ° C.
It was dried at a temperature of 120 ° C. for 3 hours, and further dried at a temperature of 120 ° C. for 1 hour.

The former was subjected to the following processing operation seven days after the molding date and the latter 24 hours after the molding time, and the finished state of the processed surface was examined.

To perform the former and the latter, a saw for woodworking was used for cutting, a plane was used for cutting, a drill for woodworking was used for drilling, and a hammer was used for nailing. As a result, there was no hindrance to all operations, and no defect was caused in the finished product. From these results, satisfactory results were achieved, and the object of use was achieved in that the solidified paper obtained by the method of the present invention could be processed according to the intended use.

As described above, according to the six examples, the method for producing a solidified paper according to the production method of the present invention is such that an aqueous solution of a silicate compound is infiltrated into paper and solidified to form a solidified paper. , Silicic acid and compounds of silicic acid (orthosilicic acid in a narrow sense), that is, it is possible to eliminate the disadvantages related to heat resistance, solvent resistance and oil resistance.

[0176]

According to the first aspect of the present invention, an aqueous solution containing an aqueous silicate-forming component composed of an alkali silicate is penetrated into paper, dried and cured to obtain an alkali silicate. Since it is solidified by using such an inorganic paper solidifying agent, it becomes a solidified paper having both heat resistance, solvent resistance and oil resistance, and can contribute to expansion of uses of the solidified paper.

According to the second aspect of the present invention, the paper material can be solidified at room temperature according to the production method in which the aqueous solution is solidified using an alkali silicate as a paper solidified material forming component. In addition, since it is a method of forming silicic acid in paper and using the silicic acid as a solidifying agent to form a solidified paper, it is easy to stabilize a solidified paper that has heat resistance, solvent resistance, oil resistance, etc. Can be manufactured. Various additives can be used as a curing agent or a curing accelerator for the aqueous silicate solution, and carbon dioxide in the atmosphere can also be used.

According to the third aspect, since the aqueous aqueous solution for forming a paper solid is configured to function with the aqueous alkali silicate solution and the additive, the aqueous solution containing the alkali silicate is penetrated into the paper. Then, when forming and manufacturing a solidified paper having both heat resistance and solvent resistance, the alkali silicate and the additive are individually actuated, or the alkali silicate and the additive are individually actuated simultaneously. The aqueous solution can be permeated into paper in combination with the paper.

By selecting the type of additive and blending it, it is possible to increase the rate of crystalline silicic acid generation from the aqueous silicic acid solution. It can also be used as an anti-condensation or sound-proof paint.

Claims (3)

[Claims] 1. An aqueous solution containing an aqueous paper solidified material forming component comprising an alkali silicate is penetrated into paper, and then dried and dried.
A solidified paper characterized by being cured. 2. A method for producing a paper solidified material having heat resistance, solvent resistance and oil resistance by infiltrating an aqueous solution containing an aqueous paper solidified material-forming component into paper, and further drying and curing it. And using an alkali silicate as the paper solidified component of the aqueous solution. 3. An aqueous paper-solidification-forming aqueous solution containing an alkali silicate as a paper-solidification-forming component for solidifying paper, wherein the aqueous paper-solidification-forming solution comprises an alkali silicate aqueous solution. An aqueous solution for forming a solidified paper, wherein the aqueous solution is configured to function with an additive.