JPH0444637B2 - - 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 inexpensive noncombustible building materials with high strength, excellent dimensional stability, and durability, and such products are used in large quantities as building materials in a wide range of fields. has been done. 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 is heading toward being 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 using asbestos, 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 something. However, lightness is an important factor for interior and exterior materials that require ease of handling, heat insulation, cost, etc., and strict requirements are also placed on dimensional stability, making them unsuitable for such applications. be. 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. Removing the asbestos constituting these lightweight plates under such conditions for sanitary reasons is said to be extremely difficult from a production technology standpoint. Board materials used for interior decoration are pasted with paper, cloth, etc., and coated, so the dimensional stability of the board materials against changes in temperature and humidity is a particularly important factor. 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 No. 49-126723 is made of a hydraulic cement binder mainly composed of glass fibers and cellulose fibers and having diatomaceous earth and pearlite as low-density fillers, and is autoclaved and stoved. However, although the present invention requires autoclave curing and is reinforced with glass fiber, durability remains a problem due to the poor alkali resistance of glass. Japanese Patent Publication No. 51-80327
The publication states that the total amount of cellulose fibers and organic synthetic fibers is 5 to 100% by weight of the fiber reinforcing material, diatomite or vermiculite is mixed as a weight reducing material, and the fiber is composed of calcium silicate with tobermolite or zonotrite. Asbestos-free products are listed. 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 No. 56-114857 uses 2 to 25% of beaten cotton having an SR of 20 to 80 degrees, and provides a thin board with a specific gravity of 1.3 to 1.9 by using organic synthetic fibers and a binder. 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 and European Patent No. 68741 disclose a technique in which cellulose fiber and porphyry silica are blended and mica or the like is used as a filler. Applicable technology is 5%
As mentioned above, it mainly consists of a large amount of cellulose fiber, and there are problems with nonflammability and dimensional stability due to the cellulose fiber. JP-A-59-73463 and JP-A-59-131551 provide plate materials that are nonflammable and have high bending strength with a specified amount of pulp, but they lack lightness and dimensional stability in dry and wet conditions. It is not satisfactory from this point of view. In addition, Japanese Patent Application Laid-open No. 185474/1983 describes fineness
It has been stated that polyvinyl alcohol-based synthetic fibers of 0.1 to 2 denier are effective in improving the bending strength of asbestos-free paper products. However, in terms of physical properties of the plate material, there are problems with lightness, dimensional stability,
There are also drawbacks to nonflammability. 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). As a result of studies to solve economic problems, it was discovered that almost satisfactory results could be obtained by combining the invention of Japanese Patent Application No. 150333/1980 with a specific inorganic lightweighting material, and this invention was developed. A patent application has already been filed on February 8, 1985. However, it has become clear that it is necessary to further improve the dimensional stability in order to make it unique as an interior material. The present inventors have arrived at the present invention as a result of intensive research aimed at improving such dimensional stability. C. Structure of the invention The gist is (1) aspect ratio of 20 or more and 30 to 30
Mica powder having a particle diameter of 5000 μm and (2) a dispersion of pulp used as necessary, (3) an inorganic molding material and (4)
After adding and dispersing the inorganic lightweighting material, (5)
Reinforcing fibers less than 0.5 denier and (6) 2 if necessary
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 the invention of Japanese Patent Application No. 150333/1983 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 intensive consideration of combinations with lightweight materials, surprisingly,
A lightweight board that is asbestos-free and has better performance and economy than conventional asbestos-cement lightweight boards without autoclave curing by simply combining the invention of the earlier patent application No. 150333/1980 with a specific lightweight material. It became possible to obtain this technology, and a patent application was filed for this technology on February 8, 1985. However, compared to asbestos-cement calcium silicate boards, which are typically used as interior and exterior materials, they do not contain asbestos, so there are no hygienic problems, and they are economical because they are not cured in an autoclave. It was found that dimensional stability, which is the most important physical property, was somewhat inferior, and the inventors of the present invention worked to improve it. Then, various studies were conducted based on the invention of the patent filed earlier on February 8th.
An effective means of increasing dimensional stability is to remove pulp, but if pulp is removed, cement particles etc. cannot be captured, and therefore problems arise in paper formability. Therefore, we investigated to find a material that does not impede dimensional stability and provides papermaking properties such as cement retention in place of pulp, and we found that it is effective to reduce the fineness of the fibers used for reinforcement to less than 0.5 denier. I discovered that. That is, instead of removing the pulp in the invention for which the patent application was filed on February 8, it is only necessary to reduce the fineness of the reinforcing fiber to less than 0.5 denier. Such an asbestos-free cement lightweight board that has no hygienic problems, is economical, and has physical properties equivalent to or better than asbestos-cement calcium silicate boards is specified in the present invention.
Products that can only be obtained from systems consisting mainly of hydraulic substances, including mica, inorganic lightweighting materials, inorganic molding materials, reinforcing fibers of less than 0.5 denier, a specified amount of pulp used as necessary, metal hydroxides, and the remainder. It is. The effects of the present invention are obtained not only by the characteristics of each component constituting the hydraulic lightweight inorganic paper product, but also by the interaction between the components, and it is believed that the effects of the present invention are obtained not only by the characteristics of each component constituting the hydraulic lightweight inorganic paper product, but also by the interaction between the components. However, if it is lacking, sufficient performance and productivity cannot be obtained. 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 a uniform dispersion of reinforcing fibers. First, 0-2% pulp, 5-50% mica, 1-
Add 20% inorganic molding material and 5 to 50% inorganic lightweighting material to water or white water, stir and disperse the slurry, add 0.2 to 5% reinforcing fiber with a fineness of less than 0.5 denier, and make sure to disperse it evenly. Stir. If necessary, a divalent or trivalent metal hydroxide is added to the slurry during the slurry preparation step or during the storage and stirring step such as CHEST. 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 product thus obtained is lightweight with an apparent specific gravity of 0.5 to 1.3 g/ ^cm3 , and is a noncombustible building material that passes the Japanese Industrial Standards (JIS A-1321).
It has extremely small dimensional change rate, good durability, and excellent mechanical properties such as bending, tension, and impact. The components constituting the present invention will be explained in detail below. First, the mica to be blended has an aspect ratio D/T of 20 or more and a particle diameter of 30 to 5000 μm.
If it has a plate-like morphology, the chemical composition, crystal shape,
There are no restrictions on production area, crushing 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 papermaking. 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. Next, the role of reinforcing fibers is to provide process passability such as the ability to capture cement particles, and to improve tensile, bending, and impact strength, which are the weak points of hydraulic inorganic cured products. The fineness of the reinforcing fiber is important in order to provide process passability, and must be less than 0.5 denier. When reinforcing fibers of less than 0.5 denier are used, inorganic molding materials, inorganic lightweight materials,
The surprising fact was discovered that due to the synergistic effect with a flocculant, it is possible to obtain the same process passability as when using asbestos without using pulp. When the fineness is 0.5 denier or more, 2% by weight
Paper making becomes difficult unless a pulp exceeding 100% is used. From the perspective of reinforcing hydraulic hardened materials, the fibers must have high tensile strength and Young's modulus, good adhesion to cement and other hydraulic inorganic materials, alkali resistance, and no health hazards. It is desirable that it be the same, and that it is also inexpensive. 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 the 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 or effect of imparting formability such as cement trapping ability, and if it exceeds 5% by weight, dispersion will be poor, making it impossible to obtain a uniform sheet and making it expensive. Fiber aspect ratio (L/D) is 200~
1500 is a preferable range in terms of both dispersibility and reinforcing properties. When such reinforcing fibers with a fineness of less than 0.5 denier are used, pulp is not required, so dimensional stability is significantly improved, nonflammability is excellent, and there are no concerns about durability caused by pulp. However, it is also possible to bring out the benefits of pulp to the extent that the problems associated with the use of such pulp are not so great. For example, pulp has the effect of improving the dispersibility of reinforcing fibers and controlling the water retention of fleece. Taking advantage of this effect, the maximum allowable addition amount without sacrificing physical properties is 2% by weight, and Canadian Friness is 30~30% by weight.
Use the one beaten to 750ml. The type of pulp may be either natural or synthetic. 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. Examples of such inorganic lightweight materials include foamed pearlite, shale, vermiculite, trachyte, obsidian, calcined diatomaceous earth, shirasu, silica, glass, etc., or a combination of two or more of them; 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 inorganic lightweighting material refers to the particle size according to JIS A5007, and the particle size is preferably 1.2 mm or less.
Preferably it is 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. In order to set the apparent specific gravity of the plate material to 0.5 to 1.3 g/cm ³ , 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 lightweighting material is preferably 5 to 50%; if it is less than 5%, the lightness of the board cannot be obtained;
If it exceeds %, 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,
Platy 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 plate powder, etc. as industrial by-products 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 hydroxide is not preferable 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 agent, inorganic molding agent, flocculant, pulp, and metal hydroxide specified above in the specified amounts, can an asbestos-cement lightweight board be produced. It is possible to obtain an economical asbestos-free lightweight board that has performance equivalent to or better than an asbestos-cement calcium silicate board with the same productivity and without the need for an autoclave. 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 Silica flour (SF powder manufactured by Nippon Heavy Chemical Co., Ltd., average particle size 0.36μ) was added as an inorganic molding material in a predetermined amount as a papermaking solid content (unless otherwise specified, the addition rate is shown below). -1) to the pulper with a slushier to give a 1% concentration of about 10
Stir and disperse for a minute. In addition, when adding pulp (Example 1, Test No. 4), pre-beaten NUKP (softwood unbleached pulp; beating degree: Canadian Freeness 100 ml) was added at the same time as the silica flour, and the mixture was stirred and dispersed for about 10 minutes. . After that, pearlite (PC light manufactured by Ube Industries, Ltd., bulk specific gravity 0.18, particle size 0.3 mm or less) and mica (Sozolite Mica 40S manufactured by Kuraray, average particle size) were used as lightweight materials.
400μ, average aspect ratio 60) was added and mixed and stirred for about 5 minutes. Thereafter, reinforcing fibers were added, mixed and stirred for about 2 minutes, and uniformly dispersed to form a slurry. The reinforcing fibers used were PVA fibers with a fineness of 0.15 dr (dr is an abbreviation for denier), a strength of 13.4 g/dr, a Young's modulus of 300 g/dr, and a fiber length of 4 mm (aspect ratio of 1000). Portland cement, which is a hydraulic substance, was added to the aqueous dispersion, stirred for 5 minutes, and then transferred to Chiest to obtain a slurry for papermaking of about 120 g/ml.
Comparative Example 1 was carried out under the same conditions as Example 1, except that one of the various additives specified in the Examples was not added. The papermaking slurry was introduced into a papermaking tank (vat) while adding an anionic flocculant (IK Flock T-210, manufactured by Ichikawa Keori Co., Ltd.) and a necessary amount of water. All coagulant addition rates are expressed as values relative to the solids in the slurry during papermaking. The slurry was made using a 60-mesh round screen, wound around a making roller, and the raw board after cutting was heated at 50°C for 24 hours, then at room temperature for 4 hours.
After being left to stand for a week, the physical properties of the product were measured and are listed in Table 1. The evaluation criteria and measurement conditions were performed using the methods 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 almost too low to form a uniform sheet, 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 A 5418 by placing the test piece in an air dryer with an agitator and drying it at 105±5℃ for 24 hours.
After drying for a period of time, the sample was placed in a desiccator whose humidity was controlled with silica gel and cooled to room temperature, and then the weight was measured and determined 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 A 1408 "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.
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 a square test piece, the occurrence of cracks in the test piece was observed. One test piece was nailed at 4 locations, and if no cracks occurred in all 4 locations, it was rated ◎, 3 locations were rated O, 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 the same as asbestos in Test No. 10 of Reference Example 1, × if there was a problem in papermaking, and ○ or △ in the middle. Product physical properties will be 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 those with flame retardancy failure or other problems with physical properties will be judged as ◎. was judged as ×, and intermediate ranks were judged as ○ and △. Hygiene was rated ○ if it did not contain asbestos, and × if it did contain asbestos. In the final overall evaluation, those that satisfied both papermaking properties and product physical properties and did not contain asbestos were given a rating of ◎, those that had any problems were given a ×, and the intermediate ranks were given a rating of ○ and △.

【table】

【table】

[Table] Example 1 is a case of a formulation consisting of the constituent elements of the present invention, and in Test Nos. 1, 2, and 3, when the amount of pearlite added as a lightweight material was changed, satisfactory paper formability and bulk were obtained. This shows that specific gravity and product physical properties were obtained. Generally, it is said that it is very difficult to obtain paper formability with non-asbestos formulations that do not use pulp at all, but in the examples of the present invention, products with satisfactory paper formability and article physical properties were obtained. Test No. 4 was a mixture of Test No. 1 with 1% pulp added, and the fiber dispersibility was significantly improved, but the dimensional stability was only slightly deteriorated. To explain Comparative Example 1, Test No. 5 is a case in which the lightweight material that is a component of the present invention is not used. , processability such as planeability became inferior. Test No. 6 was a case in which mica was not added, and in this case, the rate of change in length was extremely large, and the surface test was also failed. Test No.7 is
This is the case when reinforcing fibers of less than 0.5 dr are not added.
In this case, the capture rate of cement etc. is extremely poor,
The raw board could not be peeled off from the making roll, and no paper-made board could be obtained. Test No. 8 was a case in which silica flour, which is an inorganic molding material, was not added, and the dispersibility of the reinforcing fibers was poor, and delamination occurred. As mentioned above, Tests Nos. 5 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. It shows that you are not getting what you are satisfied with. 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. Test No. 10 is an asbestos-cement perlite board, which was produced in the same manner as in Example 1 using the formulation shown in Table-1. Also, test No. 11 is
In the case of asbestos cement calcium silicate board,
Paper-making was carried out in the same manner as in Example 1 using the formulations shown in Table-1. However, it was autoclaved at 175℃. From Table 1, Example 1 has superior paper formability and product properties compared to Comparative Example 1, and is superior to Test No. 10 of Reference Example 1 using asbestos. It is clear that almost the same result as Test No. 11 was obtained. In any case, there is nothing other than the example that satisfies all of the interior and exterior aspects from the viewpoints of hygiene, economy, and product properties. Example 2, Comparative Example 2 The fineness of the reinforcing fiber and its addition rate were changed, and the paper-making conditions were otherwise as in Test No. 3 of Example 1. The reinforcing fibers used in Example 2 and Comparative Example 2 were
For PVA fiber, its fiber properties and addition rate are shown in the table below.
This is shown in 2. Although the bending strength of Example 2 and Test No. 12 was slightly lower due to the fiber addition rate of 1%, the results were satisfactory in both cases. In Comparative Example 2, the fineness was large, so the capture rate of solids such as cement was low, and there was a problem in paper formability.

【table】

[Table] Example 3, Comparative Example 3 The bulk specific gravity and particle size of pearlite used as a lightweight material were changed. Test No. to prevent particle destruction.
The stirring time was set to 1 minute only when adding No. 18 pearlite. The test was the same as in Example 1 except that the particle size of pearlite as a lightweight material shown in Table 3 was changed.
It was conducted under the same conditions as No. 3. The results are summarized in Table 3.

【table】

[Table] Test Nos. 16 and 17 of Example 3 are the results when pearlite was used after being crushed to a predetermined particle size. Satisfactory papermaking properties and product properties were obtained in both cases. The small product of Test No. 16, which has a smaller particle size, has better surface smoothness. Test No. 18 of Comparative Example 3 is a case where pearlite with a large particle size is used. During papermaking, floating of pearlite particles and some delamination occurred. In addition, the appearance of the product surface was poor. Example 4, Comparative Example 4 Sozolite mica (manufactured by Kuraray Co., Ltd.) was used as the mica, and the mica was pulverized and classified to change the aspect ratio and addition rate as shown in Table 4. Other than the above, the paper was made in exactly the same manner as Test No. 3 of Example 1. The results are shown in Table-4. However, the shape of mica used with an aspect ratio of 60 has an average diameter of 500 μm, and the shape of mica with an aspect ratio of 20 has an average diameter of 20 μm.

【table】

[Table] Test Nos. 19 to 21 of Example 4 are the results when the mica addition rate was changed. The rate of change in length became smaller as the mica addition rate increased, and the dimensional stability improved. The physical properties of the products were also good. Test No. 22 of Comparative Example 4 shows that when the aspect ratio of mica is small, the properties of mica cannot be exhibited.
The rate of change in length was slightly large, indicating that the flame retardant property was rejected. Test No. 23 was a case in which the amount of mica added was small, and although the papermaking was good, the dimensional change rate was slightly large, and the flame retardance was rejected. Test No. 24 is a case where the addition rate of mica is increased. In this case, mica accounts for the majority, which inhibits the dispersibility of fibers during papermaking and also reduces the ability to capture solids such as cement. However, the green sheet lost its caking properties and became crumbly, making continuous papermaking operation difficult. As described above, the methods other than the examples have some problems and are not preferable. D Application The asbestos-free hydraulic lightweight inorganic paper product 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, Setsukou slag boards, It can also be used as a substitute for decorative laminates, etc. Due to the fact that it does not contain asbestos and has excellent product quality, it can be 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 tiles, etc. It is expected that the applications will further expand. 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)

[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 0 to 2%, and the fineness is less than 0.5 denier. 0.2-5% reinforcing fiber,
5-50% inorganic lightweighting material, 1-50% inorganic molding material
A hydraulic lightweight inorganic paper product with an apparent specific gravity of 0.5 to 1.3 g/cm ^3, consisting of 20% divalent or trivalent metal hydroxide and 0 to 10% and the remainder mainly hydraulic inorganic material. . 2 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 lightweight inorganic paper product according to claim 1, which is mica powder having a particle diameter of 30 to 5000 μm. 3 The fineness of the reinforcing fiber is less than 0.5 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 or more per denier. The hydraulic lightweight inorganic paper product according to any one of claims 1 to 2, which has a Young's modulus of 90 g or more per denier. 4. The hydraulic lightweight inorganic paper product according to any one of claims 1 to 3, wherein the reinforcing fibers are polyvinyl alcohol-based or polyacrylonitrile-based fibers. 5 The inorganic lightweight material has an apparent bulk specific gravity of 0.3 g/cm ³
The hydraulic lightweight inorganic paper product according to any one of claims 1 to 4, which is an inorganic foam having a particle size of 1.2 mm or less. 6 Inorganic lightweight materials are foamed pearlite, shale,
Any one of claims 1 to 5, which is an inorganic foam powder of vermiculite, trachyte, obsidian, calcined diatomaceous earth, or a balloon of shirasu, silica, glass, etc., or a combination of two or more thereof. Hydraulic lightweight inorganic paper products described in . 7. The inorganic molding material according to any one of claims 1 to 6, wherein the average particle diameter or, in the case of a fibrous material, the average fiber length is 1 x 10 ^-2 to 1 x 10 ^-5 mm. Hydraulic lightweight inorganic paper product. 8. The hydraulic lightweight inorganic paper product according to any one of claims 1 to 7, 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. 9. The hydraulic lightweight inorganic paper product according to any one of claims 1 to 8, wherein the divalent or trivalent compound is a hydroxide of aluminum, iron, magnesium, or zinc. 10 Pulp Canadian friness is 30-750
The hydraulic lightweight inorganic paper product according to any one of claims 1 to 9, which is ml. 11 0-2% pulp, 5-50% mica, 1-
0.2-5% reinforcing fibers with a fineness of less than 0.5 denier are added to a slurry in which 20% inorganic molding material and 5-50% inorganic lightweighting material are added, stirred and dispersed in water or white water.
and further add divalent or trivalent metal hydroxides so that the slurry contains 0 to 10% of the slurry, and the remainder mainly contains hydraulic inorganic substances to create a papermaking slurry. , to the papermaking slurry
A wet papermaking method for a hydraulic lightweight inorganic product having an apparent specific gravity of 0.5 to 1.3 g/cm ^{3 ,} which is characterized in that papermaking is carried out while adding a flocculant of 20 to 500 ppm. 12. The wet papermaking method for a hydraulic lightweight inorganic product according to claim 11, wherein the mica powder has a mica aspect ratio (D/T) of 20 or more and a particle diameter of 30 to 5000 μm. 13 The fineness of the reinforcing fiber is less than 0.5 denier,
The wet papermaking method for a hydraulic lightweight inorganic product according to any one of claims 11 to 12, wherein L/D is 200 to 1500, tensile strength is 5 g or more per denier, and Young's modulus is 90 g or more per denier. 14 The reinforcing fiber is polyvinyl alcohol (hereinafter referred to as
14. The wet papermaking method for a hydraulic lightweight inorganic product according to any one of claims 11 to 13, which is a PVA (abbreviated as PVA) type fiber or a polyacrylonitrile (hereinafter abbreviated as PAN) type fiber. 15 The apparent bulk specific gravity of the inorganic lightweighting material is 0.3 g/cm ³
The wet papermaking method for a hydraulic lightweight inorganic paper product according to any one of claims 11 to 14, which is an inorganic foam having a particle size of 1.2 mm or less. 16 Inorganic foam powder in which the inorganic lightweighting material is any one or a combination of two or more of foamed pearlite, shale, vermiculite, trachyte, obsidian, calcined diatomaceous earth, or balloons such as shirasu, silica, glass, etc. A wet papermaking method for a hydraulic lightweight inorganic papermaking product according to any one of claims 11 to 15. 17. Hydraulic properties according to any one of claims 11 to 16, wherein the inorganic molding material has an average particle diameter or, in the case of a fibrous material, an average fiber length of 1 x 10 ^-2 to 1 x 10 ^-5 mm. Wet papermaking method for lightweight inorganic products. 18 Claim 11, wherein the inorganic molding material is an inorganic powder made of silicic acid, silicate, or carbonate.
A wet papermaking method for a hydraulic lightweight inorganic product according to any one of items 1 to 17. 19 A compound having a divalent or trivalent atomic valence is
A wet papermaking method for a hydraulic lightweight inorganic product according to any one of claims 11 to 18, which is a hydroxide of aluminum, iron, magnesium, or zinc. 20 Pulp Canadian friness is 30-750
20. A wet paper-making method for a hydraulic lightweight inorganic product according to any one of claims 11 to 19, wherein the amount is ml.