JPH0444636B2 - - Google Patents

Description

[Detailed description of the invention]

A: Technical Field of the Invention The present invention relates to a hydraulic lightweight inorganic paper product that has excellent dimensional stability, flame retardance, and mechanical performance without using asbestos, and a manufacturing method for obtaining the paper product. It is. B. Prior Art and its Problems Hydraulic inorganic paper products are composites whose main components are fibrous materials such as asbestos and hydraulic substances such as cement, as typified by asbestos-cement boards. The main manufacturing method is to add fiber components such as asbestos and hydraulic binding components such as cement to water together with other additives to make a 5-30% by weight water dispersion (papermaking slurry), and then roll this into balls. It is made into a product by papering it on a screen or fourdrinier, dehydrating it, molding it, curing it, and drying it. This method is highly productive with simple equipment, and can provide high strength, excellent dimensional stability, durable, and inexpensive noncombustible materials, and such products are used in large quantities in a wide range of fields as building materials. It is used. The role of asbestos in hydraulic inorganic paper products is
These include imparting formability such as capturing solid content such as cement particles, and improving the physical properties of the cement board, such as improving bending strength, dimensional stability, nonflammability, and durability. Furthermore, asbestos is a very cheap material. The role of asbestos in inorganic paper products containing asbestos is extremely important, and it is said that such inexpensive products with excellent physical properties would not be possible without the presence of asbestos. The excellent properties of asbestos are that it is a fibrillar material, has high affinity with hydraulic substances, has high strength and Young's modulus, is an inorganic fiber, and has high water retention. Due to etc. On the other hand, asbestos-containing dust is generated in the air when asbestos is produced, when products containing asbestos are manufactured, processed, installed, and even used after installation. In recent years, it has become clear that fine asbestos dust, if inhaled into the human body, can cause lung cancer, etc., and its use is gradually being restricted by laws and regulations, and there are even signs that it will be banned.
Furthermore, asbestos-producing countries are unevenly distributed in certain countries, and there is also the problem of resource depletion. Under such circumstances, it is strongly desired to provide a hydraulic inorganic paper product that does not contain asbestos and has the same high productivity and performance as when asbestos is used, instead of a hydraulic inorganic paper product that contains a large amount of asbestos. ing. In order to meet such needs, we have made an invention and proposed the result as Japanese Patent Application No. 150333/1982. That is, it is a hydraulic inorganic paper product containing pulp, mica, an inorganic molding material, reinforcing fiber, and cement as essential components, and a method for manufacturing the same. It is possible to get things. However, since light weight is an important factor for interior and exterior materials that require ease of handling, heat insulation, cost, etc., the above invention is unsuitable for such applications. On the other hand, asbestos cement lightweight boards containing asbestos include, for example, asbestos perlite boards of JIS A-5413,
JIS A-5414 pulp cement board, JIS A-5427
There is a pulp cement perlite board. Although such products contain a large amount of asbestos, they have low strength and poor dimensional stability, and even now, improvements are desired. In addition, JIS A-5418 asbestos cement calcium silicate board is an excellent interior and exterior material that has been autoclaved and has good dimensional stability.
However, it remains hygienic and economical because it contains asbestos and requires autoclave curing. From a sanitary standpoint, it is said to be extremely difficult to remove the asbestos that constitutes these lightweight boards under such conditions from a production technology standpoint. In the field of interior materials, where lightweight boards are mainly used, the dimensional stability of the board against changes in temperature and humidity is particularly important, as various types of cloth are pasted and coated. Asbestos-free cement lightweight boards have been attempted in the prior art, but they have various drawbacks. For example, the invention described in JP-A-49-126723 is made of a hydraulic cement binder mainly composed of glass fibers and cellulose fibers and having diatomaceous earth and nacre as low-density fillers, and is autoclaved and stoved. However, although it requires autoclave curing and is reinforced with glass fiber, durability remains a problem due to the poor alkali resistance of glass.
JP-A No. 51-80327 states that the total amount of organic synthetic fibers such as cellulose fibers is 5 to 100% of the reinforcing material.
Asbestos-free products are described which are composed of calcium silicate with tobermolite or zonotrite, with the admixture of diatomite or vermiculite as lightening agents in weight percent. However, the obtained plate material may contain a large amount of organic matter, cracks occur when heated, and its nonflammability is not satisfactory. The same applies to dimensional stability. JP-A-56-114857 is 20~
Using 2-25% of beaten cotton with 80°SR, organic synthetic fibers and binders provide a thin board with a specific gravity of 1.3-1.9. In particular, asbestos substitutes include beaten cotton and gelling agents such as bentonite, which are used in combination with flocculants to prevent loss of solid content. However, the product may contain as much as 4 to 15% cellulose fiber, resulting in poor dimensional stability and insufficient flame resistance. British Patent Publication No. 2101645 discloses a technique in which cellulose fiber and silica are blended and mica or the like is used as a filler. This technology is based on a large amount of cellulose fiber of 5% or more, and there are problems in paper manufacturing such as cement yield, and furthermore, there are problems with product properties such as nonflammability and dimensional stability due to cellulose fiber. . In any of the above-mentioned known techniques, it is impossible to obtain a satisfactory asbestos-free, hydraulically lightweight, material-free paper product. Based on the asbestos-free hydraulic inorganic paper product of Japanese Patent Application No. 59-150333, the present inventors have investigated the problems of current asbestos-containing hydraulic lightweight inorganic paper products, namely hygiene and quality issues (particularly dimensional stability). The present invention was developed as a result of intensive research aimed at solving economic problems. C. Structure of the invention The gist is (1) aspect ratio of 20 or more and 30 to 30
After adding and dispersing (3) an inorganic molding material and (4) an inorganic lightweighting material to a dispersion of mica powder having a particle diameter of 5000 μm and (2) pulp, (5) reinforcing fibers and (6) )2
Hydraulic lightweight inorganic paper-made products made by adding a hydroxide of a valent or trivalent metal and further adding (7) a hydraulic inorganic material such as cement to a paper-making slurry while adding (8) a flocculant, and the like. It is a manufacturing method. The present inventors proposed Japanese Patent Application No. 59-150333 based on the same idea as the present invention of combining various components. However, since light weight is an important factor in interior and exterior applications that require ease of handling, heat insulation, and economic efficiency, it was found to be unsuitable for such applications. Therefore, as a result of earnestly considering combinations with lightweight materials, we surprisingly found that by simply combining a specific lightweight material with the invention of the earlier patent application No. 150333/1980, it was asbestos-free and did not require autoclave curing. Together, it has become possible to obtain a lightweight board with superior performance and economy than the conventional asbestos-cement lightweight board. That is, it has become possible to obtain an asbestos-free cement lightweight board having the characteristics of high bending strength, excellent dimensional stability, nonflammability, low cost, and no hygienic problems. Regarding dimensional stability, it was expected that the addition of lightweighting materials would reduce the bulk specific gravity of the plate material and increase its water absorption rate, so it would deteriorate. However, in the present invention, although the reason is unknown, it has been found that by adding a lightweighting material to the patent application No. 150333/1987, the dimensional stability is improved and it is possible to obtain an asbestos cement calcium silicate board. . In other words, it is intended only for systems mainly composed of mica, pulp, inorganic lightweight materials, inorganic molding materials, reinforcing fibers, divalent or trivalent metal hydroxides as required, and the remainder mainly hydraulic substances specified in this application. We have discovered that this can be achieved. The effects of the present invention are
A hydraulic inorganic paper product is obtained not only by the characteristics of each component but also by the interaction between the components, and if even one component within the scope of the present invention is missing, the product will not be sufficient. Performance and productivity are not achieved. The structure of the present invention and its effects will be described in more detail below. First, in order to obtain a papermaking slurry that can be made without using asbestos at all, it is necessary to obtain uniform dispersion of reinforcing fibers. First, 1 to 5% pulp is uniformly dispersed in water or white water, and this slurry is mixed with 5 to 50% mica, 1 to 20% fine powder as an inorganic molding material, and 5 to 50% pulp as an inorganic molding material.
Add inorganic lightweighting material to make a uniform dispersion. The order in which the above substances are added does not need to be specified. Add reinforcing fibers with a fineness of 0.5 or more to this slurry.
It is important to add and disperse 0.2 to 5%.
If necessary, this slurry may contain divalent or trivalent
Adding a hydroxide of a metal with valence.
For example, fine aluminum hydroxide particles are added. Finally, by adding the remaining hydraulic inorganic material, which is mainly cement, and stirring, a papermaking slurry in which reinforcing fibers are uniformly dispersed can be obtained. By diluting such a papermaking slurry with white water and adding a coagulant during papermaking, it is possible to stably produce paper while maintaining the water level with a solid content capture rate of 90% or more. The following products are produced using conventional methods; however, autoclaving is not necessary for curing, and steam curing at room temperature to 100°C or air dry curing may be used. The inorganic paper products obtained in this way are lightweight with an apparent specific gravity of 0.5 to 1.3 g/ ^cm3 , are noncombustible building materials that pass Japanese Industrial Standards (JIS-A-1321), and have an extremely low dimensional change rate. It is small, has good durability, and has excellent mechanical properties such as bending, tension, and impact. The components constituting the present invention will be explained in detail below. First, the first mica to be blended has an aspect ratio D/T of 20 or more and a particle diameter of 30~30.
As long as it has a plate-like shape of 5000 μm, there are no restrictions on chemical composition, crystal form, place of origin, pulverization method, etc. For example, it is appropriately selected from muscovite, phlogopite, biotite, mica, soda mica, and synthetic mica. In particular, sozoolite mica from Canada is extremely suitable due to its morphology. When D/T is less than 20, the shape becomes close to granular, the flatness of mica is lost, and the effect of dimensional stability is reduced. The average particle diameter of mica used in the present invention is required to be 30 to 5000 μm. Although the reason is unknown, when the thickness is less than 30 μm, the surface test of the nonflammability test has no effect, and its contribution to the dimensional change rate is small. On the other hand, even if it is larger than 5000 μm, although it is effective for surface testing and dimensional change rate, it cannot be used because it may cause precipitation in the vat and cause problems during paper making. The addition rate of mica is preferably 5 to 50%. If it is less than 5%, it will meet the Japanese Industrial Standards (JIS A-
1321), and its contribution to the dimensional change rate is small. Moreover, if it is added in excess of 50%, precipitation may occur in the vat during paper making, or delamination of the paper fleece may occur, making it difficult to obtain a good inorganic paper product. In terms of the physical properties of the inorganic paper product, it is preferable that the amount of pulp be as small as possible since it may impair the nonflammability or deteriorate the dimensional stability of the inorganic paper product. However, it is not allowed to use paper-made cotton. The content of the pulp of the present invention should be 1 to 5% by weight.
If the content of pulp is less than 1% by weight, the ability to trap particulate matter will be reduced, and if it exceeds 5% by weight, nonflammability and dimensional stability will be impaired and delamination will occur easily. The type of pulp may be either natural or synthetic. The reinforcing fiber improves the tensile, bending, and impact strengths, which are the weak points of the hydraulic inorganic cured product. The fibers must have the following conditions: high tensile strength, high Young's modulus, good adhesion to cement and other hydraulic inorganic materials, alkali resistance, no health hazards, and low cost. It is desirable that The most preferable reinforcing fibers that meet the above conditions are polyvinyl alcohol (hereinafter abbreviated as PVA) fibers, and polyacrylonitrile fibers (hereinafter abbreviated as PVA).
(abbreviated as PAN) is also preferably used. In addition, amide fibers, aramid fibers, carbon fibers, alkali-resistant glass fibers, etc. can also be used. These reinforcing fibers must have a tensile strength of 5 g or more per denier and a Young's modulus of 90 g or more per denier. In addition, if the surface has been modified by chemical or physical means to improve its adhesion to hydraulic inorganic substances, even fibers that are inherently hydrophobic and have poor adhesion, such as polyolefin fibers, will have the same strength and Young's modulus as described above. If the value is greater than or equal to , it can be sufficiently used in the present invention. The ratio is 0.2 to 5 for the solid content of papermaking slurry.
% by weight, preferably 1 to 3% by weight. If it is less than 0.2% by weight, there will be no reinforcing effect, and if it exceeds 5% by weight, dispersion will be poor and a uniform sheet will not be obtained.
It becomes even more expensive. The preferred range of fineness is 0.5 to 20 deniers. Also, the aspect ratio of the fiber (L/
D) is preferably in the range of 200 to 1500 in view of both dispersibility and reinforcing properties. The inorganic lightweight material reduces the apparent bulk specific gravity of the plate material. For this purpose, the additive must be lightweight, must be inorganic from the viewpoint of nonflammability, and must be particulate from the viewpoint of paper formability and smoothness. Such inorganic lightweight materials include any one or a combination of two or more of balloons such as foamed pearlite, shale, vermiculite, trachyte, obsidian, calcined diatomaceous earth, shirasu, silica, and glass, and inorganic foam. Powder can be used. The apparent bulk specific gravity of the additive material is preferably 0.3 g/cm ³ or less, and if it is larger than that, it will not contribute to reducing the weight of the board material. The particle size of the inorganic lightweighting material is preferably 1.2 mm or less as defined in JIS A5007, preferably 0.6 mm or less. If the particle diameter becomes larger than 1.2 mm, the lightweighting material will float in the slurry, which is undesirable because problems such as hindering paper forming properties and impairing the smoothness of the plate material will occur. The apparent specific gravity of the board is 0.5 to 1.3 g/cm ³
In order to achieve this, it is necessary to specify the addition rate of the specified lightweighting material within a range that does not impair paper formability. The addition rate of the weight-reducing material is preferably 5 to 50%; if it is less than 5%, the lightness of the plate material cannot be obtained, and if it exceeds 50%, the paper formability deteriorates, which is not preferable. A more preferred range is 10-35
%. Next, an inorganic molding material is a diameter or length of 1×
10 ^-2 - 1 x 10 ^-5 mm particles or fibrous matter,
By adding this substance, (a) the dispersibility of the reinforcing fibers is improved, and (b) the coagulation performance is synergistically improved by using the pulp and reinforcing fibers, inorganic lightweight material, and cement flocculant together. It has been found that papermaking properties can be improved by increasing cement retention and providing an appropriate amount of water. Furthermore, when forming the green sheet, (c) improving the lamination properties of the paper-made fleece, (d) preventing water leakage on the making roll, (e) preventing cracks and wrinkles on the making roll and cracking during unfolding, ( f) It was found that it also has effects such as providing surface smoothness and moldability during press molding. The amount of such inorganic molding material added is 1 to 20% by weight. If it is less than 1% by weight, the effect will not be exhibited, and 20
If the weight percentage is exceeded, the capture ability of cement will decrease,
The water retention becomes excessive and the formability on the making roller deteriorates. Average particle size is 1×10 ^-2 ~1
×10 ^-5 mm The reason for this is that if it is more than 1 × 10 ^-2 mm, the effect of adding the molding material will not be exhibited, and if it is less than 1 × 10 ^-5 mm, labor and energy will be required for crushing and classifying, which will increase the cost. It is expensive, and it is not economical because it passes through the cylinder during paper making. The types of inorganic molding materials are selected from natural limestone powder, heavy charcoal, charcoal, calcium carbonate such as white charcoal, light charcoal obtained by synthesis, calcium carbonate called ultrafine charcoal, and other basic ones. Powders made of carbonates such as magnesium carbonate and dolomite can be used. Furthermore, silicate compounds represented by clay minerals, such as natural kaolin, clay, ball clay, waxite clay, pyrofluorite, bentonite, montmorillonite, nontronite,
Temporary or thin plate-like materials such as saponite, sericite, zeolite, nephelinsinite, and talc;
Furthermore, fibrous or acicular materials such as attapulgite, sepiolite, and wollastonite can be used. Furthermore, synthetic aluminum silicate and synthetic calcium silicate can also be used as synthetic products. Examples of silicic acid include natural products such as diatomaceous earth and silica powder. As synthetic products, hydrated fine silicic acid, anhydrous fine silicic acid, what is called white carbon, silica dust, silica fume, limestone, fly ash, slate board powder, etc., which are industrial by-acids or wastes, can also be used. The inorganic molding material used in the present invention is non-foamed (non-porous) and is different from the above-mentioned inorganic lightweight material in this respect. It goes without saying that the inorganic molding material does not contain mica. Next, divalent or trivalent hydroxides include hydroxides of aluminum, iron, magnesium, and zinc. aluminum hydroxide, iron hydroxide,
The finer the particles of magnesium hydroxide and zinc hydroxide, the more preferable they are, and it is particularly preferable that they exist in colloidal form. The amount added must be within a range of less than 10%, if necessary. The combination of the present invention has a relatively large amount of organic matter added, and is compliant with the Japanese Industrial Standards (JIS A-
1321) "Flame Retardant Test Methods for Building Interior Materials and Construction Methods" states that if the base material test exceeds 810℃ and fails grade 1 flame retardant, the metal hydroxide must be contained within a range of less than 10% by weight. If added within the range, it becomes class 1 flame retardant and can be certified as a noncombustible building material under the Building Standards Act. If it is not added, it will be flame retardant class 2 and will be semi-nonflammable. Addition of more than 10% by weight of such metal hydroxides is not preferred because it causes cracks in the plate material. The flocculant may be a common flocculant. It may be organic, inorganic, anionic, nonionic, or cationic, but anionic polymer flocculants that are commonly used as cement flocculants are preferably used. The amount of coagulant used is preferably 20 to 500 ppm based on the solid content of the papermaking slurry. If it is less than 20ppm, the effect will be poor, and if it is more than 500ppm, the cohesive force will be too strong and the aggregates will become large flocs, or the water-based properties will be too strong and the difference in head during paper making will not be able to be corrected, resulting in the formation of a uniform sheet. is difficult. Furthermore, it causes disadvantages such as contaminating the felt and impairing productivity. Only by combining the mica, reinforcing fiber, inorganic lightweighting material, inorganic molding material, metal hydroxide compound, pulp, and flocculant in the specified amounts as described above, it is possible to produce products equivalent to asbestos-cement lightweight boards. It is possible to obtain an economical asbestos-free lightweight board that has the same performance as an asbestos-cement calcium silicate board without the need for heat and autoclaving. The reason for this is not clear, but it is thought that there is a synergistic effect, as each product has a surprisingly greater effect than expected from the effect of each product alone. Finally, hydraulic inorganic substances that can be used in the present invention include the following. A typical example is Portland cement, which includes ordinary Portland cement, medium heat Portland cement, early strength Portland cement, ultra early strength Portland cement, white Portland cement, and sulfate-resistant Portland cement.
Blast furnace cement types A and B are used as mixed cements.
Type, C type, fly attachment type A, B type,
There are C type, silica cement type A, B type, and C type. Special cements such as alumina cement, super quick-hardening cement, colloid cement, expansive cement, and oil well cement are used. In addition, it is also possible to use semi-hydrated plaster using gypsum, a mixed hydraulic material of hydrated plaster and slag, magnesia, etc. Basically, any hydraulic material may be used. It is also possible to replace a part of the hydraulic inorganic substance with other substances depending on the purpose, and this is included within the scope of the present invention. For example, calcium sulfoaluminate-based and lime-based materials can be used as expandable admixtures, and phenol, epoxy, polystyrene, polyethylene, and polypropylene foams and blowing agents can be used as organic lightening agents. Example 1, Comparative Example 1, Reference Example 1 Pre-beaten NUKP (softwood unbleached pulp; degree of beating is Canadian Freeness 100ml) was added to a pulper with a sludge so that the solid content of papermaking was 2%, and the slurry concentration was adjusted. It was stirred and dispersed at 1.8% for 10 minutes. Silica flour (SF powder manufactured by Japan Heavy Chemical Industry Co., Ltd.: average particle size) was then used as an inorganic molding material.
A predetermined amount of 0.36μ) (unless otherwise specified, the addition rate is shown in Table 1 below) was added to this slurry, and after mixing and stirring for about 10 minutes, perlite (PC light manufactured by Ube Industries, Ltd.) was added as a lightweighting material. Bulk specific gravity 0.18,
particle size 0.3mm or less) and mica (Kuraray Sozolite Mica 40S: average particle size 400μ, average aspect ratio
60) was added and mixed and stirred for about 5 minutes. Thereafter, reinforcing fibers were added and mixed and stirred for about 2 minutes to uniformly disperse and form a slurry. The reinforcing fiber used was
Made of PVA fiber with a fineness of 1.6 dr (DR stands for denier) and strength.
13.5g/dr, Young's modulus 320g/dr, fiber length 6mm,
It has an aspect ratio of 460. Portland cement, which is a hydraulic substance, was added to the aqueous dispersion, and after stirring for 5 minutes, the mixture was transferred to Chiest to obtain a slurry for papermaking of about 120 g/ml.
Comparative Example 1 is the same as Example 1 except that one of the various additives specified in Example is not added.
The same conditions were used. The slurry for papermaking was treated with an anionic flocculant (IK Flock T manufactured by Ichikawa Keori Co., Ltd.).
-210) and the necessary amount of split water were added to the papermaking tank (vat). At this time, the addition rate of the flocculant to the solid content of papermaking was 150 ppm. Note that in Reference Example 1, since the properties of the slurry were different, the slurry was as described in Table 1. The slurry was made using a 60-mesh round screen and wound around a making roller.The green boards after cutting were kept at 50°C for 24 hours and then at room temperature for 4 weeks, and the physical properties of the products after curing were measured. Evaluation criteria,
The measurement conditions were as described below. Dispersibility refers to the state of dispersion of fibrous substances, and when the papermaking slurry is drawn up into a round screen, the uneven state on the round screen is observed, and ◎ is a very good dispersion state with few bumps, and ◎ is a very good dispersion state with few bumps. The poor dispersion state was marked as x, and the poor dispersion was divided into two ranks and marked as ○ and △. Next, the water level in the vat is ◎ when it is possible to make a sufficiently uniform sheet, and when the water level is barely level and a uniform sheet cannot be made, or when the water level is so bad that the papermaking slurry overflows from the vat. It was qualitatively judged as ×, and intermediate ranks as ○ and △. The capture rate of solids such as cement and inorganic molding materials is calculated from the slurry concentration in the papermaking tank before papermaking (W ₁ ) and the concentration of wastewater discharged through a circular screen (W ₂ ) (1 - ^W2 _W1 ) x 100 It was calculated as a percentage. Delamination was qualitatively determined by manually peeling off the layers of the raw board after being rolled. Even if you apply force to peel off layers of fleece, the interlayers are unclear and it is difficult to peel off: ◎, the state where it peels off easily is ×, and the two ranks are ○ and △.
And so. Bulk specific gravity is determined in accordance with JIS A5418 by placing the test piece in an air dryer with an agitator, drying it at 105±5°C for 24 hours, then placing it in a desiccator adjusted with silica gel and cooling it to room temperature. Measure the weight and use it as the dry weight (W) g. Next, measure the length, width, and thickness, and calculate the volume (V) cm ³ . The bulk specific gravity was determined using the following formula. Bulk specific gravity = W/V The bending strength was measured according to JIS A1408 "Bending test method for architectural boards" and was expressed as the average value in the papermaking direction (vertical direction) and the direction perpendicular thereto (horizontal direction). If the capture rate of hydraulic substances, etc. changes, the blended amount of reinforcing fibers will essentially change, so in order to compare the true reinforcing properties, the capture rate of solids such as hydraulic substances, etc. will be changed.
The bending strength has been corrected to be 100%. The impact strength is a value measured only in the vertical direction without notches according to the Izod test method of JIS K-7110. The length change rate is based on JIS A-5418, and after being left to air dry for one month, the length is measured after drying at 60℃ overnight, and the length after soaking in water at 20℃ overnight is measured. The rate of change from . The flame retardancy test was conducted in accordance with JIS A-1321 ``Flame retardant test method for building interior materials and construction methods'', and a base material test and a surface test were conducted to determine whether the flame retardancy was 1st grade or 2nd grade. The nailing test for workability evaluation was conducted on a side of 30 cm.
The occurrence of cracks in the test piece was observed when nails with a diameter of 1.9 mm were nailed to a wooden post at 1 cm from each corner on the diagonal of the square test side. One test piece was nailed at 4 locations, and if no cracks occurred in all 4 locations, it was rated ◎, 3 locations were rated ○, 1 to 2 locations were Δ, and all cracks were rated ×. The sawing property test was to see how well the material was cut by hand using a household saw. A piece that could be easily cut to the end without any edge chipping or cracking with light force was rated as ○, and a piece with edge chipping or cracking was rated as ×. In the planerability test, the chamfering after saw cutting was done using a household plane with light force, and when the chamfered part was finished neatly, it was evaluated as ○, and when it was not, it was evaluated as ×. The paperability was evaluated as ◎ if it was comparable to asbestos in Test No. 10 of Reference Example 1, × if there was a problem in papermaking, and ○ or △ in the middle. The physical properties of the product are judged as ◎ if the asbestos cement pearlite board or asbestos cement calcium silicate board of Reference Example 1 Test No. 10 and 11 or better is ◎, and the product does not pass the flame retardant test or has other problems with the physical properties. The items were judged as ×, and the intermediate ranks were judged as ○ and △. Hygiene was rated ○ if it did not contain asbestos, and × if it did contain asbestos. The final overall evaluation is ◎ if it satisfies both papermaking properties and product physical properties and does not contain asbestos, × if there are problems with either, and ○ if there is a problem in either of them.
It was judged as △.

【table】

【table】

[Table] Example 1 is a formulation consisting of the constituent elements of the present invention, and Test Nos. 1, 2, and 3 are formulations in which the added amount of lightweight pearlite is changed, but the target paper formability and bulk specific gravity are respectively and product physical properties were obtained. Test No. 4 of Comparative Example 1 was a case in which the lightweighting material, which is a component of the present invention, was not used, and the product had a high bulk specific gravity and was a heavy plate material, resulting in poor workability. Test No. 5 was a case in which mica was not added, and the rate of change in length was extremely large, and the surface test was also failed. Test No. 6 was a case in which no pulp was added, and the cement capture rate was low, causing problems in paper formability. Test No. 7 was a case in which no reinforcing fibers were added, and the bending strength was low and the workability was poor. Test No.8
This is the case where silica flour, which is an inorganic molding material, was not added, and the dispersibility was poor and some delamination occurred. As mentioned above, Tests Nos. 4 to 8 of Comparative Example 1 show that if any one of the five essential components other than the hydraulic substance of the substances constituting the present invention is missing, both paper formability and product physical properties will be affected. I can't find anything that satisfies me.
Test No. 9 of Reference Example 1 is the result of the data of Test No. 1 of Example 1 of Japanese Patent Application No. 59-150333 and a supplementary test. Also, test No. 10 is asbestos 20%, pulp 2
This is a case in which an asbestos-cement pearlite board consisting of 20% pearlite and the remainder Portland cement was made in the same manner as in Example 1, with only the composition changed.
Test No. 11 was an asbestos cement calcium silicate plate made in the same manner as in Example 1. However, the composition is shown in the table.
As described in 1, autoclave curing was performed at 175°C. From Table 1, Example 1 has superior paper formability and product physical properties compared to Comparative Example 1, and Reference Example 1 using asbestos
Results were superior to Test No. 10 and almost equivalent to Test No. 11. As shown in Comparative Example 1, if even one component of the present invention is missing, it is not possible to obtain paper formability or product properties comparable to those containing asbestos. In any case, there is no material other than the example that satisfies all of the interior and exterior materials from the viewpoints of hygiene, economy, and product properties. Example 2, Comparative Example 2 The bulk specific gravity and particle size of pearlite used as a weight reducing material were changed. Tested to prevent particle destruction
The stirring time was set to 1 minute only when pearlite was added in No. 14, and the other conditions were the same as in Test No. 3 of Example 1. Test Nos. 12 and 13 of Example 2, and Test No. 14 as Comparative Example 2 are shown in Table 2.

【table】

[Table] In Test Nos. 12 and 13 of Example 2, crushed pearlite was used. Satisfactory papermaking properties and product properties were obtained in both cases. The smaller one used in Test No. 12 had better surface smoothness, but the bulk specific gravity was slightly higher. Test No. 14 of Comparative Example 2 used pearlite with a large particle size. During papermaking, floating of pearlite particles and some delamination occurred. In addition, the appearance of the product surface was poor. Example 3, Comparative Example 3 Sozolite mica (manufactured by Kuraray Co., Ltd.) was used as the mica, and as shown in Table 3, the aspect ratio was changed by pulverization and classification, and the addition rate was changed. The paper was made in exactly the same manner as Test No. 3. The results are shown in Table 3, with Example 3 being within the scope of the present invention and Comparative Example 3 being outside the range. However, the mica shape used has an aspect ratio of 60 and has an average diameter of 500 μm.
Those with an aspect ratio of 20 have an average diameter of 20 μm.

【table】

[Table] Test Nos. 15 to 16 of Example 3 are cases where the mica addition rate was changed within the scope of the present invention. The rate of change in length became smaller as the addition rate increased, and the dimensional stability improved. All other physical properties of the product were good. Test No. 18 of Comparative Example 3 showed that even if the amount of mica added was within the range of the present invention, if the aspect ratio was small, the characteristics of mica could not be fully exhibited, and the rate of change in length was large. Flame retardancy indicates failure. Test No. 19 was a case where the amount of mica added was small, and although the paper formability was good, the dimensional change rate was still large and the flame retardance was rejected. In test No. 20, when the addition rate of mica was increased, mica occupied the majority, the dispersibility of fibers during papermaking was inhibited, the ability to capture solids such as cement was reduced, and the It lost its caking properties and became crumbly, making continuous operation difficult. As described above, the methods other than the examples have some problems and are not preferable. Example 4, Comparative Example 4 Paper making was carried out in the same manner as in Test No. 3 of Example 1, except that the type and amount of reinforcing fibers were changed. However, when the amount of reinforcing fibers added was 3% or more, aluminum hydroxide was added as shown in Table 4. The type of reinforcing fiber is 1.8 denier, strength 13.5
g/d, Young's modulus 330 g/d, fiber length 6 mm high strength PVA fiber, 2.0 denier, strength 4.5 g/d, Young's modulus 76 g/d, fiber length 6 mm low strength PVA fiber,
2.4 denier, strength 8.5 g/d, Young's modulus 150 g/
d. Using a total of 4 types of high strength PAN fibers with a fiber length of 6 mm and low strength PAN fibers with a denier of 3.0 denier, strength of 3.3 g/d, Young's modulus of 31 g/d, and fiber length of 6 mm.
The results are shown in Table-4. In Example 4, the bending strength of Test No. 21 was slightly lower at 70 Kg/cm ² due to the small addition rate, but all results were satisfactory. However, the comparative example has some problems. In Test No. 25, even with high-strength PVA fibers, almost no reinforcing performance was observed when the addition rate was low. The same thing happened with the high-strength PAN fiber in test No. 27. Test Nos. 26 and 28 are cases in which a large amount of low-strength fiber is added. Paper making was possible, but dispersion was poor and some delamination occurred. The bending strength was also low compared to the amount added, resulting in poor economic efficiency.

【table】

[Table] D Applications The asbestos-free hydraulic lightweight inorganic paper products obtained by the present invention can be used in existing asbestos cement calcium silicate boards, asbestos cement perlite boards, asbestos slate soft boards, pulp cement boards, pulp cement perlite boards, It can be used as a substitute for Setsukou slag boards and their decorative boards. Due to the fact that it does not contain asbestos and has excellent product quality, it is used as interior and exterior materials for buildings and ships, such as curtain walls, fireproof partition walls, exterior wall panels, siding materials, and in some cases, single Western roof tiles. can be expected to expand further. Another advantage is that, depending on the type, particle size, and addition rate of mica specified in this application, the pattern visible on the surface of the board can be attached to wallpaper or cloth as an interior material, or it can be used as a fabric without coating the surface. have.

Claims (1)

[Scope of Claims] 1 Mica is 5 to 50% by weight based on the solid content of the papermaking slurry (hereinafter referred to as weight% based on the solid content of the papermaking slurry unless otherwise specified), pulp is 1 to 5%, and the fineness is 0.5 denier or more. 0.2-5% reinforcing fiber, 5-50% inorganic lightweighting material, 1-20% inorganic molding material
%, a metal hydroxide having a divalent or trivalent valence of 0 to 10%, and the remainder mainly consisting of hydraulic inorganic material, and has an apparent specific gravity of 0.5 to 1.3 g/cm ³ . 2. The hydraulic inorganic paper product according to claim 1, wherein the reinforcing fibers have a fineness of 20 denier or less. 3 The aspect ratio of mica (the ratio of the diameter of mica to its thickness, hereinafter abbreviated as D/T) is 20 or more,
The hydraulic inorganic paper product according to claim 1, which is mica powder having a particle diameter of 30 to 5000 μm. 4 The fineness of the reinforcing fiber is 0.5 to 20 denier, the fiber aspect ratio (the ratio of the length of the fiber to its diameter, hereinafter abbreviated as L/D) is 200 to 1500, and the tensile strength is 5 g per denier. The hydraulic inorganic paper product according to claim 1, which has a Young's modulus of 90 g or more per denier. 5. The hydraulic inorganic paper product according to claim 1, wherein the reinforcing fibers are polyvinyl alcohol-based or polyacrylonitrile-based fibers. 6 The inorganic lightweight material has an apparent bulk specific gravity of 0.3 g/cm ³
The hydraulic inorganic paper product according to claim 1, which is an inorganic foam having a particle size of 1.2 mm or less. 7 The inorganic lightweight material is foamed pearlite, shale,
The hydraulic inorganic material according to claim 1, which is an inorganic foam powder of any one or a combination of two or more of vermiculite, trachyte, obsidian, calcined diatomaceous earth, or balloons such as shirasu, silica, and glass. Paper-made products. 8. The hydraulic inorganic paper product according to claim 1, wherein the inorganic molding material has an average particle diameter, or in the case of a fibrous material, an average fiber length of 1×10 ⁻² to 1×10 ⁻⁵ mm. 9. The hydraulic inorganic paper product according to claim 1, wherein the inorganic molding material is an inorganic powder of any one or a combination of two or more of silicic acid, silicate, and carbonate. 10 A compound having a divalent or trivalent atomic valence,
The hydraulic inorganic paper product according to claim 1, which is a hydroxide of aluminum, iron, magnesium, and zinc. 11 Pulp Canadian friness is 30-750
The hydraulic inorganic paper product according to claim 1, which is ml. 12 1~5% pulp, 5~50% mica, 1~
0.2 to 5% of reinforcing fibers with a fineness of 0.5 denier or more are added to a water or white water dispersion prepared by stirring and dispersing 20% of an inorganic molding material and 5 to 50% of an inorganic lightweighting material, and then divalent or trivalent A hydroxide of a metal having a valence is added to the slurry in an amount of 0 to 10%, and the remainder is mainly a hydraulic inorganic material to prepare a papermaking slurry.
A wet paper-making method for hydraulic inorganic products, which is characterized by paper-making while adding 500 ppm of a flocculant. 13. The wet papermaking method for a hydraulic inorganic product according to claim 12, wherein the reinforcing fiber has a fineness of 20 denier or less. 14. The wet papermaking method for a hydraulic inorganic product according to claim 12, wherein the mica powder has an aspect ratio (D/T) of 20 or more and a particle diameter of 30 to 5000 μm. 15 The fineness of the reinforcing fiber is 0.5 to 20 denier,
13. The wet papermaking method for a hydraulic inorganic product according to claim 12, wherein L/D is 200 to 1500, tensile strength is 5 g per denier or more, and Young's modulus is 90 g or more per denier. 16. The wet papermaking method for hydraulic inorganic products according to claim 12, wherein the reinforcing fibers are polyvinyl alcohol-based or polyacrylonitrile-based fibers. 17 The apparent bulk specific gravity of the inorganic lightweighting material is 0.3 g/cm ³
13. A wet papermaking method for a hydraulic inorganic paper product according to claim 12, which is an inorganic foam having a particle diameter of 1.2 mm or less. 18 Pearlite, shale, foamed with inorganic lightweight materials,
The hydraulic inorganic material according to claim 12, which is an inorganic foam powder of any one or a combination of two or more of vermiculite, trachyte, obsidian, calcined diatomaceous earth, or balloons such as shirasu, silica, and glass. Wet papermaking method for papermaking products. 19. Wet paper-making method for hydraulic inorganic products according to claim 12, wherein the average particle diameter of the inorganic molding material or the average fiber length in the case of fibrous material is 1 x 10 ^-2 to 1 x 10 ^-5 mm. . 20 Claim 12, wherein the inorganic molding material is an inorganic powder made of silicic acid, silicate, or carbonate
Wet papermaking method for hydraulic inorganic products as described in Section 1. 21 A compound having a divalent or trivalent atomic valence is
A wet papermaking method for a hydraulic inorganic product according to claim 12, which is a hydroxide of aluminum, iron, magnesium, and zinc. 22 Pulp Canadian friness is 30-750
13. A wet paper-making method for a hydraulic inorganic product according to claim 12, which is ml.