JPH02192443A - Co-refined pulp-mountain cork and production of reinforced hydraulic inorganic molded article using the same - Google Patents

Abstract

PURPOSE:To perform a sheet-forming process in high efficiency and to improve the strength and heat-resistance of the obtained cured article by co-refining pulp and mountain cork to obtain a composite pulp material, producing an aqueous slurry from the pulp material and a hydraulic inorganic substance, making a sheet from the slurry and curing the product. CONSTITUTION:Pulp and mountain cork are subjected to co-refining treatment and an aqueous slurry is produced from the product and a hydraulic inorganic substance. The slurry is formed in the form of a sheet and cured to obtain a reinforced hydraulic inorganic molded article. The co-refining of pulp and mountain cork is carried out by the mechanical treatment of pulp and mountain cork in water to effect the disintegration, crushing, beating, etc. Preferably, the amount of mountain cork is 0.1-10 pts.wt. per 1 pt.wt. of pulp and the total amount of pulp and mountain cork in water is 3-65% in terms of solid in the above co-refining process. The hydraulic inorganic substance is e.g. cement, silica, diatomaceous earth, blast furnace slag, fly ash, lime and gypsum.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pulp-wood refining material and a method for producing a reinforced hydraulic inorganic molded body using the same.

Conventional summer technology, for example, Portland cement was replaced with hydraulic inorganic material, i.e.
So-called asbestos slate boards, which use asbestos as a binding material and reinforcing fibers, calcium silicate boards, slag gypsum boards, etc. can be mass-produced typically by paper-making using the beech-nick method followed by autoclave curing. Because it is nonflammable and has excellent strength, it is widely used as a building material. However, in recent years, the use of asbestos has been restricted because it causes so-called asbestos pollution not only in the manufacturing environment of building materials containing it but also in the usage environment.

Therefore, in recent years, the production of fiber-reinforced hydraulic inorganic molded bodies without using asbestos has been widely studied. For example, Tokuko Sho 63
-19465 discloses that together with pulp and polyvinyl alcohol fiber, seviolite, a type of mountain bark, is used as a freeness adjusting material to make an aqueous slurry, and this is made into a paper.
A method of manufacturing an inorganic molded body by curing has been proposed.

In addition, JP-A-61-31337 discloses that, in addition to mica, pulp, reinforcing synthetic fibers, and hydraulic inorganic substances, fibrous or acicular sepiolite, attapulgite, wollastonite, etc. are used to improve the dispersibility of reinforcing fibers and improve papermaking. A method has been proposed for producing a hydraulic inorganic molded body by paper forming using the slurry in order to improve its freeness.

However, in general, when using a valve, for example, a cement board is porous and has poor cold resistance, weather resistance, etc. On the other hand, even if polyvinyl alcohol fiber is used, the heat resistance is poor. In addition, in the production of fiber-reinforced hydraulic inorganic molded bodies,
As mentioned above, the mountain bark is only used to improve the freeness of the slurry and the dispersibility of reinforcing fibers. Moreover, even when using such mountain bark, if the mountain bark with long fiber length is used, even if the slurry can be made into a sheet, the resulting cured product will have white streaks made of mountain bark fibers remaining on the surface. On the other hand, when using powdered mountain bark,
However, it has not been possible to obtain a practical cured product because delamination tends to occur in the resulting cured product.

The inventors of the present invention intend to use valves as reinforcing fibers and
As a result of intensive research to solve the above-mentioned problems in the production of hydraulic inorganic molded bodies using mountain bark as one of the raw materials, we found that by refining the valve together with mountain bark in advance, the two coagulate inseparably from each other. However, it is possible to obtain a composite valve material, and by making it into a papermaking slurry together with a hydraulic inorganic substance, it can be made into a sheet with good drainage properties in the same way as when asbestos is used as a reinforcing fiber. First, it was discovered that the resulting cured product has excellent strength and heat resistance, and furthermore, does not cause peeling between the eyebrows, leading to the present invention.

The valve-bark co-refining material of the present invention for refining is obtained by co-refining a valve and a barb.

In addition, the method for producing a fiber-reinforced hydraulic inorganic molded body according to the present invention includes co-refining the valve and the mountain skin in advance, and then making this into an aqueous slurry together with a hydraulic inorganic substance.
It is characterized by making paper and curing it.

The mountain skin used in the method of the present invention is a clay mineral having a large number of active hydroxyl groups on the surface, and refers to sepiolite, which is hydrated magnesium silicate, attapulgite, or palygorskite, which is hydrated magnesium aluminum silicate. It is called cork, mountain leather, mountain wood, etc. Meerschaum is also a type of mountain bark. The shape of the mountain bark used in the present invention is not limited in any way, and in addition to fibrous shapes, any of the shapes of lumps, mud, and powder can be used. Further, the mountain skin used in the present invention may contain talc, calcite, dolomite, magnesite, basic magnesium carbonate, silicic acid components, etc. as host rocks and interstones.

In the present invention, it is preferable that the mountain bark be coarsely crushed in advance before being refined together with the valve. Coarse crushing is
It can be carried out by any means, either wet or dry, but when using lumpy mountain bark, it is preferable to coarsely crush it into 2 to 3 meshes or less.

The bulb used in the present invention is usually an unbleached bulb made of coniferous or broad-leaved wood, but cotton, cotton, hemp, pineapple leaves, Basho leaves, interlayer hair, straw, boar, mitaka, etc. can also be used. . In addition, depending on the manufacturing method of the valve, the valve may be a sulfide valve, a craft valve, a ground valve, a chemical valve, a thermomechanical valve,
Chemothermomechanical valves and the like are known, and any of them can be used.

In the present invention, co-refining of the valve and the mountain skin involves disintegrating the valve and the mountain skin by mechanical treatment in water.
Refers to re-crushing, beating, or refining. In this co-refining, preferably 0.1 to 10 parts by weight of the valve is used for 1 part by weight of the valve, and in the co-refining, the valve and the valve are preferably mixed in the total amount of water. is used so that the solid content concentration is 3 to 65%.

When the amount of mountain skin used is less than 0.1 part by weight per 11 parts by weight of Pal, the amount of mountain skin attached to the valve is too small, resulting in insufficient formation of a composite as described below. For example, in the Hachnik method, the freeness may be poor or delamination may occur in the resulting cured product. On the other hand, the amount of mountain bark used is 10% per 1 part by weight of pulp.
When the amount is more than parts by weight, for example, in the papermaking process,
In addition to making it difficult to wind up the sheet on a making roll, which hinders smooth production, it also becomes difficult to increase the bulk specific gravity of the resulting sheet. etc., which is not desirable. Furthermore, the reinforcing effect of the valve may be reduced.

In co-refining, fresh water including industrial water, tap water, underground water, river water, etc. is preferably used. The water used for co-refining can be reused.

Co-refining can also be performed using paper-made white water. In this case, it is desirable to treat the white water by adding acid, aluminum sulfate, clay, etc. after beating the pulp in advance or before co-refining.

Co-refining of the pulp and the pulp can be carried out using an ordinary glue refiner. Such refiners include, for example, fret mills, co-kneaders, continuous kneader 1 paper heaters, paper refiners including disc refiners, cone refiners, and drum refiners, Keday mills, speed line mills, etc. Examples include mills, double disc refiners, stamp mills, etc. Also, the top
Finer, fibre, etc. can also be used as needed. Furthermore, in the present invention, co-refining may be performed using different types of refiners, if necessary.

Co-refining is carried out in water at room temperature up to 100°C. Generally, the higher the temperature, the faster co-refining can occur.

The degree of co-refining depends on the pulp and bark used, and cannot necessarily be specified uniformly, but the degree of co-refining depends on the pulp and bark used. Co-refining is desirable.

Pre-beaten waste paper valves can also be used as valves. In this case, the co-refining valve according to the present invention can also be produced by previously beating the mountain bark alone, mixing the previously beaten mountain bark and waste paper, and further beating if necessary. In the present invention, as described above, mixing pre-beaten mountain bark and waste paper pulp is also included in the pulp-vessel refining process.

Furthermore, in the present invention, when co-refining the valve and the mountain skin, organic synthetic fibers may be present together. In this manner, the obtained hydraulic cured product of the mountain skin-valve co-sofing material containing organic synthetic fibers can be made even higher in strength and more heat resistant.

Examples of the organic synthetic fibers used include polyvinyl alcohol fibers, polyacrylonitrile fibers, polyamide fibers, polyester fibers, polyethylene fibers, polypropylene fibers, polyvinylidene chloride fibers, polyvinyl chloride fibers, and polytetrafluoroethylene fibers. Among these, polyvinyl alcohol fibers or polyacrylonitrile fibers are preferably used. Such reinforcing fibers usually have a fiber length of 0.1 to 25 mm and a fiber diameter of about 1 μm.
A material having a molecular weight of 0.2 m to 0.2 m is preferably used.

In particular, when co-refining pulp and mountain bark, polyvinyl alcohol fibers form an inseparable composite with pulp and mountain bark, and can provide a hydraulically cured product with extremely high heat resistance. .

In the present invention, when co-refining the bulb and the mountain skin, calcium silicate fibers called wollastonite, sheetzulite, etc., platy mica such as tobermorite, muscovite, vermiculite, glass fibers, Rock wool, various ceramic fibers, etc. may also be used together.

Alternatively, these fibers may be added after co-refining of the valve and husk. These inorganic fibers also help improve the weather resistance, shrinkage resistance, heat resistance, etc. of the resulting cured product, and also help reduce the amount of pulp and reinforcing synthetic fibers used.

As described above, after co-refining the pulp and mountain bark, the resulting composite is agglomerated using a flocculant as necessary, and then centrifugation, filter press, cloth high-pressure slurry squeezer, etc. By concentrating and separating the slurry, the pulp-husk co-refining material according to the present invention can be obtained as an aqueous slurry. If necessary, it may be dried to form a substantially solid state.

In the present invention, as the flocculant, any of conventionally known inorganic flocculants and organic polymer flocculants can be used. Therefore, as the inorganic flocculant, for example, polyaluminum chloride, ferrous sulfate, ferric sulfate, ferric chloride, bread earth sulfate, sodium aluminate, polyaluminum sulfate, etc. can be used. When such an inorganic flocculant is used, a flocculating aid such as slaked lime, soda ash, sodium silicate, bentonite, fly ash, etc. may be used in combination.

Furthermore, as the organic polymer flocculant, both natural flocculants and synthetic flocculants can be used.

Examples of natural organic polymer flocculants include guar gum,
Non-ionic materials such as sodium alginate, starch, gelatin, chitosan, root juice of A. spp. Mention may be made of aqueous and anionic flocculants.

As for the synthetic organic polymer flocculant, both so-called medium degree of polymerization (molecular weight of several thousand to 1000 yen) and high polymerization degree (molecular weight of several hundreds of thousands to 1000 yen) can be used. Specific examples include anionic flocculants such as sodium polyacrylate, its partial hydrolyzate, polyacrylamide partial hydrolyzate, acrylamide/sodium acrylate copolymer, polyvinylimidacillin, polyalkylaminoacrylate, Examples include cationic flocculants such as polyalkylaminomethacrylate and Mannich modified polyacrylamide, and nonionic flocculants such as polyacrylamide and polyethylene oxide. However, among these, nonionic flocculants such as polyacrylamide and polyethylene oxide with a high degree of polymerization are particularly preferred.

Even if it is applied to pulp or organic synthetic fibers after being individually beaten, for example, polyethylene oxide cannot aggregate the fibers. but,
Pulp and organic synthetic fibers co-refined with mountain bark are coagulated and sedimented with polyethylene oxide. Therefore, it is confirmed from these properties that the co-refining material according to the present invention is a composite of pulp or synthetic fiber and mountain bark.

In addition, when agglomerating the pulp-husk co-refining, a sizing agent may be used in combination. Such sizing agents include starch-based sizing agents such as carboxymethyl cellulose, methyl cellulose, hydroxyl methyl cellulose, etc., funori, gelatin, glue, soluble keratin,
Examples include tanman, konnyaku, polysaccharides, polyvinyl alcohol, vinyl acetate emulsion, styrene-butadiene rubber latex, and the like.

In particular, when producing a calcium silicate plate, it is advantageous to use an emulsion binder in combination to improve the workability of the resulting calcium silicate plate.

In this way, by co-refining the pulp and the pulp in water, the pulp adheres to the surface of the pulp fibers or becomes entwined with them, forming a kind of composite that cannot be separated from each other. . Therefore, in the bulb-hull refining material obtained in this way, even if it is made into a water slurry of extremely low concentration, for example, about 0.1% by weight, the pulp and the hull will not be separated from each other. In addition, in such a composite, the clay mineral yamaha adheres to the surface of the pulp fibers and protects the fibers. It has excellent heat resistance and strength.

Furthermore, such a reinforcing fiber-skin composite can adsorb the hydraulic inorganic substance by stirring and mixing it with the hydraulic inorganic substance described below in water, and in particular, in the presence of a flocculant (coagulates,
Therefore, it can be easily filtered with good drainage through a wire mesh of about 20 meshes, and papermaking can be carried out efficiently using the conventional Hachnik method.

Also, bulbs are generally not stained by basic dyes. However, although there are some differences depending on where it is produced, mountain bark usually has solid acidity and is dyed with basic dyes. Here, since the bulb-bark co-refining material according to the present invention is a mutually inseparable composite, it is uniformly dyed with an alkaline dye.

When co-refining the valve and the mountain skin, a surfactant may be used in combination, if necessary. As the surfactant, water-soluble nonionic or anionic surfactants are preferably used.

Next, the production of the pulp-reinforced hydraulic inorganic hardening material according to the present invention will be explained.

In the method of the present invention, the above-described valve-mount refining material is made into a water slurry, and, as in the case of manufacturing asbestos slate boards by the papermaking method, a hydraulic inorganic substance is added to the water slurry, if necessary. A flocculant, an inorganic filler, etc. are added, stirred and mixed to prepare an aqueous slurry for papermaking, and filtered paper is produced. There is no problem in preparing this slurry for papermaking even if so-called white water is used.

Examples of the hydraulic inorganic substance used in the method of the present invention include various cements typified by Portland cement, silica stone, diatomaceous earth, blast furnace slag, fly ash, lime, and gypsum. For example, if Portland cement is used as the hydraulic inorganic material, a cement slate board can be obtained, and if silica, diatomaceous earth, lime, etc. whose main component is calcium silicate is used as the hydraulic inorganic material, a calcium silicate board can be obtained. By using slag, gypsum, lime, etc., slag gypsum boards can be obtained. It goes without saying that in addition to this, gypsum boards, magnesium carbonate boards, calcium carbonate boards, etc. can also be obtained by appropriately selecting a hydraulic inorganic substance.

In the method of the present invention, such a flocculant is used in an amount of about 3 to 300 ppm of the solid content in the papermaking slurry when producing a molded body by the papermaking method.

In the present invention, when preparing a slurry for papermaking,
If necessary, calcium silicate fibers such as wollastonite and sheetzulite as described above, platy mica such as tobermorite, muscovite, and vermiculite,
Glass fibers, rock wool, various ceramic fibers, etc. may also be added to the slurry. Further, organic synthetic fibers as described above may be added.

The valve is designed to ensure the non-flammability of the resulting molded product.
It is usually used in an amount of 2 to 5% by weight based on the solid content of a slurry for papermaking, but it can be used in an amount exceeding 5% by weight if necessary.

Furthermore, in the method of the present invention, an inorganic filler may be used in combination. Examples of such inorganic fillers include fibrous inorganic substances such as wollastonite, ettrin guide, sheet dry, aluminum hydroxide, and basic magnesium carbonate, flaky mica, vermiculite, pearlite,
Examples include whitebait balloons, glass fibers, slag gypsum boards, and the like. Such an inorganic filler is generally used in an amount of 1 to 20% by weight, preferably 2 to 10% by weight, based on the solid content of the slurry.

Further, in the method of the present invention, when preparing the slurry for papermaking, a sizing agent as described above may also be used.

In particular, when producing a calcium silicate plate, it is advantageous to use an emulsion binder in combination to improve the workability of the resulting calcium silicate plate. The thickener is usually used in an amount of 0.1 to 5% by weight based on the solid content of the slurry.

In the method of the present invention, the solid content concentration in the papermaking slurry is usually in the range of 2 to 30% by weight, preferably in the range of 3 to 15% by weight.

The slurry for papermaking obtained as described above is made into a sheet by a papermaking method similar to the production of asbestos slate, and then
By curing, an inorganic molded body can be obtained. As the papermaking method, the Hachinik method (round net papermaking method) or the Fourdrinier method can be used, but the Hachinik method is usually used.

That is, the pulp and mountain bark according to the present invention, if necessary, a co-refining material made of organic synthetic fibers, and a hydraulic inorganic substance are fed into a CHEESTER, diluted with white water, and then a flocculant is added, if necessary. While forming flocs,
Transfer to Hachinik aircraft. The number of batts is not particularly limited, but usually 3 to 4 batts are used. A round mesh of 60 mesh is usually used, but a coarser mesh may be used depending on the characteristics of the slurry.

After forming into a sheet, it may be compressed with a press, or a pattern may be added to the surface.

In the present invention, the paper-made sheet may be naturally cured, but may also be cured in an autoclave. Autoclave curing is a process in which a paper-made sheet is heated with high-temperature, high-pressure saturated steam in an autoclave to harden the hydraulic inorganic material that makes up the sheet through a hydrothermal reaction. In particular, in the production of gypsum slag boards, autoclave curing is preferably employed because it allows fibrous ettringite to develop well.

In the present invention, the curing temperature is usually 100°C or higher, preferably 110°C or higher, although it depends on the hydraulic inorganic material used.
-180°C, particularly preferably 130-180°C
The temperature range is 160°C. In autoclave curing,
The pressure is usually in the range of 1-10 kg/cd. Moreover, the curing time is usually in the range of 4 to 24 hours.

On the other hand, the solid content of the filtrate produced by papermaking of the sheet is precipitated by, for example, anionic coagulation, and the coagulated material is recovered together with cement and can be reused. Also,
White water can be reused as dilution water when mixing cement.

In the method of the present invention, the paper-making efficiency can usually be 70 to 97%, although it depends on the paper-making machine, the paper-making speed, the mesh degree of the wire mesh, the filler used, etc.

As described above, according to the present invention, by co-refining the pulp and the pulp, the pulp adheres to or entangles the surface of the pulp fibers and coagulates inseparably from each other. It forms a type of complex. In such a composite, a clay mineral called ash adheres to the surface of the pulp fibers and protects the fibers, and in the same way as in the production of hardened products using asbestos as the conventional reinforcing fiber, pulp-reinforced hydraulic inorganic A cured body can be produced.

That is, such a composite adsorbs a hydraulic inorganic substance by stirring and mixing the hydraulic inorganic substance in water, and in particular,
Since it coagulates well in the presence of a coagulant, it can be easily filtered with good drainage, and papermaking can be carried out efficiently using the conventional Hachnik method.

Further, according to the present invention, a cured product produced by using such a composite is free from glabellar peeling (in addition, it has excellent heat resistance and strength).

Further, the paper sheet can also be cured in an autoclave.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 (Manufacture of pulp-bark refining material) 45 g of unbeaten softwood pulp was added to 1.5 kg of water, and the mixture was beaten with an experimental paper beater for about 3 hours until the degree of freeness was approx. 40
A beaten pulp of °SR was obtained.

On the other hand, 45 g of Chinese Seviolite was lined into a cotton shape.
was added to 1.5 kg of water and subjected to Kaiso beating for about 30 minutes, and then 1.5 kg of water was further added to sediment and remove coarse unpulverized impurities such as dolomite and calcite.

The respective slurries of the above-mentioned beaten pulp and ruled sepiolite were placed in a large vat, stirred and mixed uniformly with a hand mixer, and then beaten again with a paper beater for 30 minutes to form a highly beaten slurry with a degree of freeness of 60.4. Obtained 6 kg.

Next, 10 ml of a separately prepared aqueous solution containing 1.5% polyethylene oxide and 0.2% hydroxyl ethyl cellulose was added to the slurry to coagulate the co-sofaed material. After decanting the supernatant,
The above-mentioned aggregate was filled into a polyethylene bag of about 40 meshes, and dehydrated using a dehydrator of a domestic washing machine to obtain a valve-bark refining material according to the present invention.

5g of Kono water-containing Harbu mountain skin refining material to 10
After drying at 0°C, the composition was determined by firing at 600°C. Before drying and firing, the moisture content was 61% by weight and sepiolite was 1.49g.

The pulp was 1.52g.

(Manufacture of hardened cement) A dispersion of 1.0 g of polyvinyl alcohol fiber (AA-1,6DX 6 mm manufactured by Unitika Kasei ■) in 50 ml of water was added to 5 g of the above-mentioned pulp-skin refining material, and 11 was added and mixed using a household mixer until the mixture became homogeneous. Next, 60 g of Portland cement, 3 g of wollastonite powder, and 500 ml of white water were added to the resulting slurry, and the mixture was stirred for 2 minutes using a household mixer. When the time required for the volume to become 1/2 of the original volume after natural filtration was determined, it was approximately 80 seconds.

Thereafter, the sheet was filtered under reduced pressure using an aspirator, and the obtained sheet was placed upside down on a filter paper and allowed to naturally cure to obtain a cured plate having a thickness of 4 sheets. The papermaking rate was 96%. Also,
The bending strength of the obtained cured plate was 313 kg/cn.

Example 2 Softwood pulp 100 beaten to 60'SR in advance
g (solid content 30%) and sepiolite extruded by adding water in advance (Need Bluff! manufactured by Shikinichi Yakuhin Kogyo ■, PMC)
W) Add tap water to 60g of molded product (50% moisture),
After the total weight was 11,200 g, the mixture was uniformly stirred and mixed using a commercial juice mixer. During this stirring and mixing operation,
There was no bubbling.

Next, 2 ml of a separately prepared aqueous solution containing 1.5% polyethylene oxide and 0.2% hydroxyl ethyl cellulose was added to the above slurry to aggregate the co-refined material, and after standing for several minutes, the supernatant liquid was decanted. . The resulting agglomerated co-refining material was filled into a bag of about 40 meshes made of polyethylene, and dehydrated using a dehydrator of a domestic washing machine to obtain a pulp-vessel co-refining material according to the present invention. Moisture was approximately 65%.

For comparison, the same beaten softwood bulb 100 as above
g (solid content 30%) and sepiolite molded body 60g (moisture 50%), add white water to make a total if 200g,
When the mixture was stirred using a commercial juice mixer, it foamed significantly and could not be mixed uniformly.

(Production of hardened cement) A dispersion in which 1.0 g of polyvinyl alcohol fiber (AA-1,6D x 6 mm manufactured by Unitika Kasei ■) was previously dispersed in 20 ml of water was added to 7 g of the above-mentioned pulp-bark refining material, and 11 was added thereto, and the mixture was stirred and mixed using a commercial mixer until the mixture became homogeneous. No bubbling occurred.

Next, Portland cement 60 was added to the resulting slurry.
g, 3 g of wollastonite powder, and 500 ml of white water were added thereto, and the mixture was stirred for 2 minutes using a household mixer, followed by the same procedure as in Example 1 to obtain a cured plate having a thickness of 4 ffI [11].

The papermaking rate was 92%. Moreover, the bending strength of the obtained cured plate was 301 kg/ctA.

Example 3 150 g of Need Plus PMC, 500 g of corrugated waste paper pulp (solid content 30%) that had been beaten to a degree of freeness of 70, and 15 kg of water were mixed using a Niagara-type test beater (Sanei Sokki ■).
Made in Japan, capacity 1231, rotation speed 50Orpm, standard drill 550
0g) and beaten for about 30 minutes.

Add 30 kg of water to the obtained slurry, and while mixing,
．． Add 11 g of 5% polyethylene oxide aqueous solution,
The co-refining material was coagulated and settled. After removing the supernatant from the slurry, a continuous centrifuge (Japanese centrifuge)
Manufactured by H-1205, capacity 51, filter cloth diameter 30cm, height approximately 16C! l, rotation speed 300 rpm) to about 120 f
The slurry was pumped and dehydrated at a rate of fi/min. After the liquid feeding was completed, the centrifugal separator was operated for about 25 minutes to complete the dehydration and obtain a cake-like co-refining material with a solid content of 22% by weight and a thickness of about 3 cm.

For comparison, only waste cardboard valves were beaten in the same manner as above, and the same amount of polyethylene oxide aqueous solution was added to the resulting slurry, but the valves did not coagulate and settle.

Examples 4 to 13 Mountain bark, bulbs, polyvinyl alcohol fibers in some cases, and water were beaten with a beater in the same manner as in Example 3, using the amounts shown in Table 1. A co-refining material was obtained in the same manner. Table 1 shows the solid content.

Example 14 15 g of each of the co-refining materials obtained in Examples 3 to 13 as a solid content and 12 grams of white water were charged into a household mixer and mixed by stirring for 1 minute. After this, 60 g of Portland cement and 1 portion of white water were added to the resulting slurry. and while stirring and mixing, add anionic surfactant (Sunfloc AH-330P manufactured by Sanyo Chemical Industries, Ltd., 1% by weight aqueous solution) 3.
Drops were added to allow the solids to flocculate.

The above water-containing coagulated sediment 12 is naturally filtered using a cylindrical filter equipped with a 32-mesh wire mesh having a diameter of 13 cm,
The linear filtration velocity was measured from the time taken to obtain filtrate 500a+1, and the freeness of each co-refining material was compared. The results are shown in Table 2.

The cake-like sheet thus obtained is dehydrated under reduced pressure,
Two sheets of this were stacked to form a laminated sheet, and immediately after that, the laminated sheet was folded after 5 days, and 28 days later, and peeling at the seams between the sheets was visually examined. No peeling was observed.

Table 2 Example 15 Unbleached softwood kraft valve (NU
KP) 300kg and 6 fish were thrown in, and the water was circulated for about 15 minutes to loosen the valve. Next, the product was refined to 60'SR using a double disc refiner, which is a paper refiner, by the Schopper-Leagsea method, and then transferred to a paper beater.

Next, 600 kg of powdered purified Seviolite (Need Plus PMCW manufactured by Shikinichi Yakuhin Kogyo ■) (water 50%) was put into the beater, mixed with the beating valve, and heated in the valve for about 15 minutes while circulating under no load. and Seviolite were co-refined.

Further, 4.0 kg of polyvinyl alcohol with a fiber length of 6 (Vinylon AA manufactured by Unitika) was added to this slurry.
After circulating for about 15 minutes, a co-refined material with polyvinyl alcohol fibers was obtained.

0.1% by weight polyethylene oxide aqueous solution 1.51 (
0.3% solids by weight) was added to the slurry obtained above, and about 5%
The co-refining material was allowed to flocculate and settle by circulating for a minute. This flocculated sediment is treated with an inclined wire mesh machine to firstly dehydrate free water, and then secondarily dehydrated with a screw press to obtain a bulb-polyvinyl alcohol fiber-Seviolite co-refining material with a moisture content of 65%. Obtained.

Example 16 Coniferous/hardwood mixture (weight ratio 25/7) in paper pulper
5) Chemithermochemical valve (CTMP) 250k
g and 5 pieces of real fishing were added and premixed for about 15 minutes. Next, after transferring to a papermaking beater (capacity 8 bottles), Sepiolite (Need Plus ML-100W manufactured by Shikinichi Yakuhin Kogyo ■)
) was put into the beater in an amount of 750 kg in terms of solid content, and circulated under a light load for about 30 minutes to obtain a slurry containing the co-refining material.

The freeness of this slurry was measured by the Schopper-Leigsee method, and the apparent freeness was approximately 58°SR.

Next, 3.2 kg of polyvinyl alcohol [11 (Vinylon AA manufactured by Unitika Corporation) with a fiber length of 6 cm was added to the slurry.
and 4 kg of alkali-resistant long glass fibers (manufactured by Nitto Boseki) with a fiber length of 6 am were added to the beater, and the mixture was heated for an additional 30 minutes.
The fibers were dispersed in the slurry by circulation under no load to obtain a slurry of co-refining material containing polyvinyl alcohol fibers and glass fibers.

A 0.1% by weight polyethylene oxide aqueous solution 21 (solid content: 0.5% by weight) was added to this slurry and circulated for about 5 minutes to coagulate and precipitate the co-refining material containing polyvinyl alcohol fibers and glass fibers. This flocculated sediment was compressed and dehydrated using a press machine combining an endless wire mesh and a caterpillar to obtain a pulp-polyvinyl alcohol fiber-Seviolite co-refining material with a water content of 67%.

Example 17 400 kg of cardboard waste paper and fishing rod 5 in waste paper pulper for paper making
M was added and stirred for about 30 minutes to disintegrate the waste paper. Next, 600 kg of pre-pulverized attapulgite was added and mixed with stirring for about 10 minutes.

Next, the waste paper and attapulgite were co-beaten using a super fiber generator, which is a type of paper refiner. As a result, the undisintegrated waste paper and the coarsely crushed acpulgite remaining in the pulper were completely beaten.

Separately, 100 kg of softwood unbleached kraft pulp was processed in the same manner as in Example 15 to obtain a softness of 55 by the Schopper-Leagsey method in a double disc refiner for papermaking.
Beaten to °SR. This was put into a papermaking naginata beater, and 3 kg of the same polyvinyl alcohol fiber as in Example 15 was also put therein and circulated for about 5 minutes to disperse it in the slurry.

In addition, a small amount of the slurry was put into an 11-capacity measuring cylinder, about 700 ml of water was added, shaken, and visually observed to find that there were no binding fibers, indicating that it was well dispersed. I confirmed that there is.

The thus obtained co-beaten product of the beaten pulp and polyvinyl alcohol fibers and the above-mentioned co-beaten product of the waste paper bulb and acpulgite were stirred and mixed for about 3 minutes in a chest with a capacity of 20 M equipped with a screw stirrer. . Next, the same polyethylene oxide aqueous solution 51 (solid content 1.0% by weight) as above was added to this, and the mixture was circulated for about 5 minutes.
A co-refining material consisting of waste cardboard, attapulgite, beaten pulp and polyvinyl alcohol fibers was coagulated and sedimented.

This coagulated sediment was dehydrated using a continuous centrifugal dehydrator to obtain a co-refining material with a water content of 60%.

Example 18 Unbleached softwood kraft valve (NUKP) 250, which had been beaten to a freeness of about 60'SR in the same manner as in Example 15.
5 kg (solid content) of real fishing rods were put into a paper pulper.

On the other hand, a molded product made by kneading Spanish Seviolite with water and extruding it (Need 1'ps PMC manufactured by Shikinichi Yakuhin Kogyo ■)
W) 500 kg (moisture 50%) was put into the above pulper and thoroughly stirred and mixed to obtain a slurry containing a pulp-sepiolite co-beating product.

Next, 40 kg of polyacrylonitrile fibers with a fiber length of 5 mm (Casimilon manufactured by Asahi Kasei Corporation) were added to this slurry and stirred for about 10 minutes to obtain a slurry containing a co-refining material consisting of pulp, Seviolite, and polyacrylonitrile fibers. .

0.1% by weight polyethylene oxide aqueous solution 5! was added to the slurry and stirred for about 3 minutes to coagulate the co-refining material. This coagulated sediment is poured onto a rotating endless wire mesh to a nearly uniform thickness, and after the free water is primarily dehydrated, a suction box is installed under the wire mesh, and the wire mesh is filtered by suction. Compression dehydration was performed using a wound roll to obtain a co-refining material with a water content of 70%.

Example 19 Beating pulp 10 with a beating degree of 50°SR1 and a moisture content of 70% by weight
0kg, Needplus PMC 30kg, 10kg of polyvinyl alcohol fiber with the same fiber length of 6- as above, and 3t of water.
was put into a pulper and co-beaten for 15 minutes to obtain a slurry.

Add 6 tons of water to this slurry, and while stirring, add 1.5 tons of water.
2 kg of aqueous polyoxyethylene oxide solution was added thereto, coagulated and sedimented, and then dehydrated to obtain a co-refining material with a water content of 70% by weight. The yield was 164 kg.

20 Put the entire amount of co-refining material and 1.5 t of white water into a pulper, stir and mix for 15 minutes, disperse the co-refining material in white water, and then add 130 kg of a mixture of papermaking sludge and wollastonite, and 80 kg of Portland cement.
0 kg and 1.5 t of white water were added and stirred and mixed for 5 minutes.

Next, through CHEST, the entire amount of the slurry was treated with a flocculant (Sanfloc AH-330P manufactured by Sanyo Chemical Co., Ltd.,
500 g of a 1% by weight aqueous solution was added, coagulated, and made into paper using a Hachnik machine, and its paper-making characteristics were investigated. The results are shown in Table 3.

For comparison, 100 kg of the same beaten pulp as above with a beating degree of 50' SR1 and a moisture content of 70% by weight, Need Plus PM
30 kg of C and 10 kg of polyvinyl alcohol fibers having the same fiber length as above were put into a pulper containing 1.5 t of white water, and stirred and mixed for 15 minutes. In this stirring and mixing operation, a large amount of bubbles were generated, so a small amount of antifoaming agent was added to defoamer, and stirring and mixing was then carried out.

Next, 130 kg of a mixture of papermaking sludge and wollastonite and 800 kg of Portland cement were added to this slurry along with 1.5 t of white water, and the mixture was stirred and mixed for 5 minutes.

Thereafter, the material was treated in the same manner as above, and paper-formed using a Hachnik machine, and its paper-forming characteristics were examined. The results are shown in Table 3.

According to the method of the present invention, drainage efficiency is high, the water level in the vat is stable, winding on a making roll is good, and delamination does not occur in the paper sheet. On the contrary,
According to the comparative example, the paper forming properties were poor, and the resulting sheet also had peeling between the eyebrows.

Table 3 Example 20 Add 30 kg of raw softwood bulb (UKP) to 1 ton of paper-made white water and heat in a double disc refiner for about 45 minutes.
Beat the pulp to obtain 50 ml of beaten pulp (Shopper bark)
A refined pulp was obtained. Approximately 250 aluminum sulfate
When g was added, the pulp liquid became cloudy and the pH of the pulp liquid decreased slightly.

Add 15% each of Needplus ML-50D and PMC (both manufactured by Shikinichi Yakuhin Kogyo ■) to this pulp liquid as a pulp.
A total of 30 kg was added in kg increments, and further co-beating was carried out for 15 minutes. After this co-beating, 2% by weight polyethylene oxide 3! was added and stirred slowly to agglomerate the co-refined material. This was dehydrated in a screw press to obtain a co-refined concentrate with a solids content of 35%.

Next, add 1 t of white water to the pulper and reduce the solid content to 60k.
After adding g of the above co-refining materials and stirring uniformly, 800 kg of cement and 130 kg of wollastonite were added.
g, 10 kg of the same polyvinyl alcohol fibers as above were added, stirred and mixed again until the mixture was homogeneous, passed through a thiester, and then made into paper in fixed amounts using a 4-vat Hachinic machine. Winding up with a making roll was also good, and the paper could be made at a papermaking rate of 92% in approximately the same time as in the production of a slate board using 5% asbestos without peeling between the eyebrows.

The raw cement board thus obtained was cured with steam to obtain a slate board that passed the nonflammability standards.

Example 21 Add 30 kg of raw conifer bulb (UKP) to 1 ton of water,
It was refined for about 45 minutes in a double disc refiner. Needplus PMC and ML-50 as mountain skin
Add 20 kg and 10 kg of D, respectively, and add 15
Co-beating was carried out for a period of minutes.

Separately, 10 kg of the same polyvinyl alcohol fibers as above were placed in a reservoir tank, and stirred in the reservoir tank until the fibers were uniformly dispersed.

An aqueous solution 31 prepared by adding 1% by weight of polyvinyl alcohol to a 2% by weight polyethylene oxide aqueous solution was added to the above reservoir tank to coagulate the co-beaten product.

This was pumped to a screw press and dehydrated to obtain a co-refining material with a solids content of 35% by weight.

When this was used for papermaking in the same manner as in Example 20, the papermaking rate was 92%. The obtained green cement board was cured with steam to obtain a slate board with a smooth surface in which polyvinyl alcohol fibers were uniformly dispersed.

Example 22 Add 40 kg of raw coniferous bulb (UKP) to water,
It was refined in a double disc refiner for about 45 minutes. This was directly dehydrated using a screw press to obtain a highly refined bulb with a solid content of 35% by weight.

Separately, 30 kg and 20 kg of Needplus PMC and ML-50D were mixed as mountain skin, and this was mixed with 55 kg of water.
0 kg were mixed and extruded using an extrusion kneader for china clay to prepare a mountain bark extract mixture.

40 kg of the high-definition bulb in solid content, 40 kg of the mountain skin extract mixture in solid content, 5 kg of the same polyvinyl alcohol fiber as above, and 50 kg of polyethylene oxide powder.
When the mixture was mixed and extruded using a clay kneader, the result was a kneaded product with only some moisture being released.
Obtained 0 kg. The solid content of this kneaded product was 46% by weight.

A small amount of polyvinyl alcohol fiber was added to the above-mentioned kneaded material in a pulper so as to have the same composition as in Example 20, and this was used to make paper in the same manner as in Example 20, resulting in a paper-making rate of 92%. The obtained green cement board was cured with steam to obtain a slate board with a smooth surface in which polyvinyl alcohol fibers were uniformly dispersed.

Patent applicant: Takeda Pharmaceutical Company Limited Kojin Co., Ltd.

Claims (2)

[Claims] (1) Pulp and mountain skin refining material made by jointly refining pulp and mountain skin. (2) A method for producing a reinforced hydraulic inorganic molded article, which comprises previously refining the pulp and mountain bark together, then making an aqueous slurry with a hydraulic inorganic substance, forming a paper, and curing it.