JPS597835B2 - Manufacturing method for sheet-shaped architectural interior materials - Google Patents

Description

Detailed Description of the Invention The present invention contains a large amount of inorganic powder that does not harden by reacting with water (hereinafter referred to as non-hydraulic), uses a thermoplastic resin emulsion as a binder, and further heat-treats the binder. The present invention relates to a method for manufacturing a sheet-like architectural interior material made insoluble in water.

More specifically, it contains a non-hydraulic inorganic powder such as gypsum dihydrate and a thermoplastic resin emulsion such as a vinyl acetate polymer as essential components, and optionally contains a blowing agent, an air entraining agent, a reinforcing material, a pigment, Form an inorganic powder slurry with additives such as plasticizers, form it into a sheet, dry it,
This relates to a method for manufacturing sheet-like architectural interior materials that is characterized by heat treatment, and its purpose is to improve water resistance,
Architectural materials such as wall covering materials, ceiling materials, flooring materials, furniture covering materials, etc., which have excellent flame retardancy, flexibility, and anti-condensation properties, as well as excellent workability such as embossing, heat insulation, and vibration-proofing properties. It is an object of the present invention to provide a sheet-like architectural interior material suitable as a material or an interior material for automobiles, etc. Traditionally, the interior of Japanese houses has been plastered with inorganic materials such as plaster or sand walls, but due to demands for diversification of design and construction costs, various interior materials have come to be used. Ta.

Typical examples are wallpaper and decorative boards made from vinyl chloride resin sheets, cloth, non-woven fabrics, processed paper, etc., but recently there has been a strong demand for these interior materials to be made non-flammable due to their flammability. I'm getting used to it. Gypsum board, asbestos, slate boards, etc. can meet the requirements in terms of noncombustibility, but they cannot be called interior materials and are instead used as part of ceiling materials. In addition to being noncombustible, architectural interior materials also have properties such as water resistance, condensation resistance, abrasion resistance, bending resistance, impact resistance, adhesion, stain resistance, sound absorption, heat insulation, feel, color, etc. There are many demands, and a material that can satisfy all of these demands has not yet been developed. The present inventors have conducted intensive research in order to improve the flame retardancy of conventionally used wallpapers, decorative plywood, etc., and to develop multifunctional materials suitable for architectural interior materials that satisfy the above requirements. As a result of stacking, a slurry containing non-hydraulic inorganic powder and thermoplastic resin emulsion as essential components, and containing other additives as necessary, is formed into a sheet shape, dried, and heat-treated. The present inventors have discovered that the sheet-like architectural interior material thus obtained has the desired multifunctionality, and have completed the present invention. In other words, in order to improve the flame retardancy of building interior materials, flame retardants such as halogens have been added to building interior materials, but there are no materials that are satisfactory in terms of the generation of toxic gas in the event of a fire and the non-combustibility effect. Essentially, it is necessary to contain a large amount of nonflammable inorganic material or to contain an appropriate amount of water.

However, it is very difficult to solidify and mold a light amount of inorganic powder with only a small amount of organic material as a binder to impart non-flammability. An effective method is to form the slurry into a slurry, form it into a sheet, and then remove the solvent by drying or the like. The solvent used in such a dry molding method is most preferably water rather than an organic solvent from the viewpoint of working environment, recovery process, fire prevention, etc. Therefore, as a binder, a water-soluble polymer or a polymer in the form of an emulsion is preferable. convenient. However, molded products using such water-soluble polymers or emulsion-like polymers as binders tend to dissolve again when they come into contact with water, and do not retain their shape. Furthermore, they are extremely sensitive to humidity and have poor dimensional stability. .

In the present invention, in order to improve this drawback, the resin itself is insoluble in water. A slurry containing thermoplastic resin emulsion such as vinyl acetate polymer and non-hydraulic inorganic powder such as dihydrate gypsum as essential components, and other additives as necessary, is formed into a sheet shape and dried. After sufficient water is removed by a heat treatment method, the resin particles forming the emulsion are heat-treated at a temperature higher than the melting temperature to fuse the resin particles together and at the same time remove the large amount of non-hydraulic inorganic powder contained in the emulsion. It was discovered that the resulting sheet-like molded product can be bonded to the body and has excellent water resistance without becoming insoluble or swollen when it comes into contact with water, and also has the flexibility of the resin itself. It is also possible to maintain the flame retardancy exhibited by containing a large amount of inorganic powder. On the other hand, conventional technology involves adding water-soluble polymers, emulsions, latex, etc. to a water slurry of hydraulic gypsum or hydraulic cement to improve the water resistance and strength of the resulting gypsum boards, cement concrete, and cement mortar moldings. is well known.

The present invention is essentially different from such a method for producing a hydraulic inorganic molded product; when a hydraulic inorganic powder is used, the resulting sheet-like product loses its flexibility and is not suitable for the intended architectural use. It cannot be used for interior materials such as It is essential that the inorganic powder used in the present invention does not react with water and harden.
It is added for the purpose of imparting nonflammability, increased weight, moldability, design, etc. Examples of the thermoplastic resin emulsion used in the present invention include vinyl acetate polymer emulsion, acrylic polymer emulsion, vinyl chloride polymer emulsion, vinylidene chloride polymer emulsion, urethane polymer emulsion, and styrene-butadiene emulsion. Examples include polymer emulsions, but vinyl acetate polymer emulsions are particularly preferred.

In addition to vinyl acetate homopolymer emulsion, the vinyl acetate polymer emulsion used in the present invention includes, for example, vinyl acetate and ethylene, various acrylic esters (methacrylic esters), acrylic acid, methacrylic acid, maleic acid, and maleic acid. esters, vinylversacic acid,
Examples include copolymer emulsions with diacentacrylamide, vinyl propionate, vinyl caproate, vinyl chloride, and the like. These thermoplastic resin emulsions have been widely used in paints, adhesives, etc., and emulsions obtained by any manufacturing method can be used, and depending on the type of emulsifier, It can be widely used without any restrictions on solid content concentration, emulsion particle size, emulsion viscosity, etc. However, if the emulsion is destroyed when adjusting the slurry after adding non-hydraulic inorganic powder, consideration must be given to adjusting the emulsion in order to improve its stability. Those having excellent physical properties such as blocking properties, mechanical properties, and flexibility are preferred, and vinyl acetate emulsions are most suitable for the sheet-like building interior material intended for the purpose of the present invention for the reasons mentioned above. In the present invention, it is also possible to use a plasticizer in order to further improve the flexibility of the sheet-shaped architectural interior material. Examples of plasticizers generally include phthalic acid and phosphoric acid esters such as dibutyl phthalate and trioctyl phosphate, and other plasticizers suitable for each thermoplastic resin used in the present invention can be used. Examples of the inorganic powder that does not harden due to reaction with water used in the present invention include gypsum dihydrate, calcium carbonate, silica sand, silica powder, kaolin, clay, talc, aluminum hydroxide, etc. However, there are two non-hydraulic inorganic powders that can satisfy the above-mentioned conditions required for a multifunctional material, such as moldability, flame retardant effect, color tone, and flexibility of the resulting sheet-like building interior material. Water plaster is the most suitable.

As dihydrate gypsum, for example, natural gypsum, phosphoric acid by-product gypsum, titanium by-product gypsum, flue gas desulfurization by-product gypsum, etc. obtained by any of the manufacturing methods can be used. Furthermore, instead of these non-hydraulic inorganic powders, it is also possible to use lightweight aggregates such as perlite, shirasu balloons, and hollow glass spheres. In addition, if necessary, organic fibers such as vinylon and nylon, inorganic fibers such as glass fiber, asbestos, and rock wool, plate materials such as mica, and glass paper, glass mat, glass cloth, asbestos, etc. Fabric materials such as paper, cheesecloth, gauze, nonwoven fabric, and paper can also be used as reinforcing materials, and various dyes,
It is also possible to use colorants such as pigments, fungicides, blowing agents, air entraining agents, foam stabilizers, thickeners, and the like. The blending ratio of the non-hydraulic powder and the thermoplastic resin emulsion used in the present invention can be changed depending on the use and purpose of the obtained sheet-like architectural interior material. It will improve, but it will become less flexible.

Sheet-shaped molded products containing about 8 to 20% by weight of thermoplastic resin in solid content are subject to Ministry of Construction Notification No. 1828 and 3417.
It is possible to provide a sheet-like architectural interior material that passes the surface test and base material test specified in the No. 2013-1 and has good flexibility, but when it is less than about 8% by weight, it becomes inflexible and brittle. comes out. On the other hand, those containing about 20% by weight or more of thermoplastic resin showed flame retardancy equivalent to semi-nonflammable in the above-mentioned combustion test, and had very good flexibility, handleability, and feel, as well as vibration-proofing properties. and is suitable as a general interior material. The method for manufacturing a sheet-like architectural interior material according to the present invention involves first adding a thermoplastic resin emulsion with an appropriate solid content concentration, water in an amount required for moldability, a plasticizer, a pigment, a blowing agent, and air entrainment as necessary. A thickener such as polyvinyl alcohol for improving moldability is added and mixed and stirred.

Next, while continuing stirring, an appropriate amount of non-hydraulic inorganic powder having an appropriate particle size and particle size distribution is gradually added to prepare a stock slurry. If necessary, various reinforcing agents are added at this stage. It may be necessary to further add water in order to adjust the moldability of the slurry after adding the inorganic powder. After defoaming or foam regulation, the slurry is formed into a sheet. Molding methods include, for example, an extrusion method, a coating method, and a dip method, and any of these methods can be used for molding. In the extrusion method, the relatively high viscosity slurry is passed from an extruder through a die to a thickness of 0.5 to 5 m77! This method is easy to dry, as it is extruded into a sheet, placed on a rotating heating drum, and dried by blowing hot air if necessary. The coating method is a method in which the relatively low viscosity slurry is applied onto a film or belt through a doctor blade or the like with a certain gap, and the slurry is sent to a dryer placed on the film or belt. The coating method dries on one side and has a slow drying speed, but if the slurry is coated directly onto the cloth-like reinforcing material instead of a film or belt, drying becomes faster. In the dip method, a continuous cloth-like reinforcing material is passed through the slurry, the slurry is applied to both sides of the cloth-like reinforcing material, and then the slurry is rolled using a roller or a spatula-like blade to obtain an appropriate sheet thickness. By scraping off the material and drying it, a cloth-like reinforcing material can be placed inside the sheet-like molded product, and drying speed can be increased by drying both sides. Next, the sheet formed by the method described above is sufficiently dried, and then sent to a hot roller, hot plate, heating chamber, etc., where it is heat-treated. The heat treatment temperature and time must be such that the thermoplastic resin emulsion particles can fuse with each other, hold the inorganic powder, and allow the resulting sheet-shaped molded product to exhibit sufficient performance. Although it varies depending on the type of resin, a temperature of 50 to 200°C for 3 to 30 minutes is appropriate. Furthermore, it is necessary to adjust the thickness of the sheet-like material to make it uniform by passing it between rollers before or after the heat treatment, and at this point it is also possible to embossing the surface if necessary. Depending on the purpose for which the sheet-shaped architectural interior material of the present invention is used, a foamed sheet with a light specific gravity may be preferable.

In order to obtain a foam type sheet, there is essentially no difference from the production method described above, but by adding an air entraining agent or a foaming agent, it is also possible to produce a highly foamed sheet with a specific gravity of about 0.1. First, in order to cause foaming by the air entrainment method, an air entraining agent such as a nonionic surfactant such as polyvinyl alcohol, potassium oleate, polyethylene glycol monolaurate, etc. is added to the slurry at a concentration of 0.0%.
If 1 to 10 parts by weight is added and stirred sufficiently, stable and minute air bubbles can be introduced. The minute air bubbles introduced by air entrainment remain stable even after forming, drying and heat treatment processes, and the specific gravity of the foam sheet can be adjusted by adjusting the amount of air entraining agent added and the stirring conditions of the slurry. be.
Next, when foaming is performed using a blowing agent, an evaporative blowing agent such as ethanol, toluene, heptane, etc. or a decomposition agent such as sodium bicarbonate, ammonium carbonate, azobisisobutyronitrile, paratoluenesulfonyl hydrazide, etc. Any type of blowing agent can be used. A blowing agent is added to the slurry in an amount of 0.1 to 10 parts by weight,
By passing through the molding, drying, and heat treatment steps in exactly the same manner as in the above manufacturing method, a foamed structure is developed in the drying or heat treatment step. In order to make foaming effective, a foaming agent with an appropriate evaporation or decomposition temperature that matches the drying and heat treatment process conditions should be selected, and the specific gravity of the foam sheet depends on the type and amount of the foaming agent added. It can be adjusted by drying and heat treatment conditions. The resulting sheet-shaped building interior material is flexible and pliable, and has excellent tensile, bending, and scratch strength as well as abrasion resistance. It can also be processed using various processing methods, including embossing, and has an excellent appearance. It can have calyxes.

In addition, it can be rolled up into long rolls, and can be bonded to metal plates, plasterboard, plywood, solid walls, etc. using an appropriate adhesive or solvent such as toluene, or by sandwiching thermoplastic resin and thermocompression bonding. be able to. The plate-like material to which the sheet-like material is glued can be cut into one piece or bent. When the sheet-like material is used as an interior material, it absorbs and releases indoor moisture. It has excellent dew condensation resistance due to its ability to absorb moisture, but since the emulsion particles are fused during the heat treatment process and become water-insoluble, there will be no dimensional changes due to moisture absorption, and it will not peel off. do not have. Since the sheet-like material contains a large amount of inorganic powder and an appropriate amount of water, it has excellent flame retardancy, and will not catch fire even if a cigarette is lit, for example. In addition, when noncombustible plate-like materials such as steel plates, asbestos slates, and gypsum boards are composited, they have sufficient performance to pass as noncombustible materials. Further, since the surface of the sheet-like material is smooth, it is hard to get dirty, and even if it becomes dirty, it is easy to remove, but since it has the ability to absorb moisture, it may be stained with ink or the like. For such uses, water permeability can be prevented by further treating the surface with a water repellent.
Even in this case, water vapor still passes through, so the anti-condensation properties are not impaired. As described above, the sheet-like material obtained by the present invention is a multifunctional material that can satisfy all of the various properties widely required as interior materials for ceilings, walls, floors, etc., and can be widely used as interior materials for buildings. It is also suitable as a covering for furniture and as an interior material for automobiles, etc. Furthermore, it can be used as a vibration-proofing material and various heat insulating materials to be attached to the housings of room coolers and motors. Hereinafter, the present invention will be specifically explained with reference to Examples; however, the present invention is not limited to these Examples in any way.

In the examples, all "parts" mean parts by weight unless otherwise specified. Example 1 Vinyl acetate-ethylene copolymer emulsion (Pamphrex 0M-4000 manufactured by Kuraray, solid content concentration 50% by weight)
After adding dihydrate gypsum powder to the slurry, enough water was added to make the water content 28% by weight, and dihydrate gypsum, which was a by-product from the flue gas desulfurization process, was dried and passed through a 32-mesh sieve. The powder was added in an amount such that the composition of the solid content in the sheet-like molded product obtained was the concentration shown in Table 1, and the mixture was stirred and mixed to obtain a slurry.

This slurry was poured onto a glass plate with a polyethylene film on its surface and air-dried indoors to a thickness of 1.5 m.
m sheets were obtained.

This sheet was heat-treated for 15 minutes at the temperature shown in Table 1 to obtain a sheet-shaped building interior material, and various physical properties shown in Table 1 were measured. Among the physical properties shown in Table 1, water retention is the water content determined by soaking a dry sample in water for 24 hours, then taking it out and measuring its weight, expressed as a percentage of the weight of the original sample. It is a value that is a parameter of water resistance and dew condensation resistance, and 30 to 10001) is preferable as an interior material. The flammability test results were obtained using a flammability test method in accordance with Ministry of Construction Notification No. 1828 and No. 3417, using a sheet-like sample pasted onto a galvanized iron plate with a thickness of 0.6 m1 using an epoxy resin adhesive. These are the test results, and bending workability refers to the cracking of a sheet-like material bonded to a steel plate when the sheet-like material is bent inward and outward at an angle of 90° by placing it on a sharp-edged metal surface plate. This shows the results of observing the condition, and those with cracks are said to be defective, and those with no cracks are said to be good. This is an evaluation of the processing performance as an interior material for heat-insulating folded steel plates, etc. Condensation resistance means that a sheet sample is pasted on the outside of a glass water tank with double-sided adhesive tape, placed in a room at a room temperature of 20°C relative temperature 65 (f), and iced water at 0°C is placed in the tank for 5 hours. This is the result of observing the condition of water droplets adhering to the surface of the sheet-like sample and the bleeding condition of the letters written with water-based ink on the surface, and if no water droplets or letters bleeding were observed on the sample surface. It was said to be good, if only the letters were blurred, it was said to be somewhat good, and if there was even a small amount of water droplets attached, it was said to be poor.
Peeling off commercially available vinyl chloride wallpaper and tough walls: 1.5
The one cut out to the thickness of a dragon was recognized as defective in this anti-condensation test. As is clear from the results shown in Table 1, the sheet material obtained by the present invention heat-treated at 1200°C or 150°C is highly flexible, has excellent bending workability, and has good dew condensation resistance. Furthermore, materials with a high content of gypsum dihydrate are recognized as noncombustible materials and are therefore suitable as sheet-like building interior materials.

On the other hand, the sheet-like sample of Comparative Example 1-1, which is not heat-treated for 5 times, has flexibility but is very brittle, lacks ease of handling, loses shape retention when left in water, and has poor water resistance, making it suitable for use in architectural interiors. It was not suitable as a material. Example 2 Using dihydrate gypsum obtained from flue gas desulfurization as a non-hydraulic inorganic powder, the engineered pine vision shown in Table 2 was used as a thermoplastic resin emulsion (thermosetting resin emulsion in Comparative Example 2-1). Using the same method as in Example 1, a sheet material having a thickness of 1.5111 and a proportion of dihydrate gypsum in the solid content of 85% by weight was obtained.

Furthermore, each sample was heat treated at 150°C for 15 minutes. Table 2 shows the physical properties of each sheet-like product obtained.

Any material using a thermoplastic resin emulsion as a binder is highly flexible and can be used as a building interior material. On the other hand, when a thermosetting resin emulsion was used as a binder (Comparative Example 2-1), it became hard and brittle, and lacked handleability, making it unsuitable as a building interior material. Example 3 Vinyl acetate-ethylene copolymer emulsion (manufactured by Kuraray, Panflex 0M5010 solid content concentration 55 weight (:
f)) 10 parts, 88% of the non-hydraulic inorganic powder shown in Table 3 (hydraulic inorganic powder in Comparative Examples 3-1 and 3-2)
part, and a polymerization degree of 1700 as a thickener to improve moldability.
, 10 parts by weight of a 10% by weight solution of partially saponified polyvinyl alcohol (Kuraray Popal 217, manufactured by Kuraray Co., Ltd.) with a degree of saponification of 88 mol%, and 26 parts of water were mixed and stirred to form a slurry with a thickness of 1 mm in the same manner as in Example 1. .5mT1L1 A sheet-like material was obtained in which the proportion of inorganic powder in the solid content was 88% by weight.

Furthermore, each sample was heat treated at 150 C for 10 minutes and then left at room temperature for 28 days before being subjected to physical property measurements. As shown in Table 3, the physical properties of the obtained sheet-like materials are as follows: When non-hydraulic phosphoric acid by-product dihydrate gypsum and silica powder were used as inorganic powders, the sheet-like materials were highly flexible and good for interior building interiors. material was obtained.

However, in this example, a product with a slightly lighter specific gravity was obtained due to the foaming effect of polyvinyl alcohol added as a thickener. On the other hand, when hydraulic gypsum hemihydrate or Portland cement is used as an inorganic powder, the moldability is good, but it is very hard, has no elongation, and is not easy to handle as a sheet material, so it is not suitable as an interior material. It's inappropriate. or,
In the case of Portland cement, there is also a problem with color tone. Example 4 In Example 3, flue gas desulfurization by-product dihydrate gypsum was used as the non-hydraulic inorganic powder, and in addition, 2.5 parts of glass fiber cut into 2 m1 length without a sizing agent was added. The slurry was prepared by stirring, stirred for a little longer to foam, and then coated onto a continuously moving polyethylene film from a doctor blade with a width of 95 (177!) and a slit width of 20 mm.

The moving speed of the film was 5.3 m/min, and the moldability was good. Next, after drying at room temperature, it was heated to 150℃ for 15 minutes.
Heat treated for minutes. Table 4 shows the physical properties of the obtained sheet-like material. It is highly flexible, has good dew-proofing properties, and has good flame retardancy, making it suitable for architectural interior materials. Thermal conductivity was measured by stacking sheet-like materials to a thickness of 6 CTL and using a linear heat source method (thermal conductivity measuring device TC-22 model manufactured by Kyoto Electronics Industry Co., Ltd.). Example
5 Vinyl acetate-ethylene copolymer emulsion (Pamphrex 0M-40001 manufactured by Kuraray, solid content concentration 50% by weight)
) 28 parts, flue gas desulfurization by-product dihydrate gypsum 84 parts, degree of polymerization 170
A slurry with a moisture content of 24% by weight was prepared by mixing and stirring 20 parts of a 10% by weight solution of fully saponified polyvinyl alcohol (Poval 117 manufactured by Kuraray Co., Ltd.) and 0.6 parts of a decomposable blowing agent (para-toluenesulfonyl hydrazide). Continuously extrude from a nozzle with a slit width of 1.511 using a screw type extruder (401t7!Lφ), and immediately
After drying on a hot plate at 150°C, heat treatment was performed at 150°C for 20 minutes to obtain a specific gravity of 0.43 and a thickness of 3. A foamed sheet material of i1 was obtained.

As shown in Table 4, this sheet-like material is highly flexible and has excellent heat insulation properties, and is suitable for interior construction materials. Example 6 In Example 5, polyvinyl alcohol had a polymerization degree of 2.
0001 A slurry was prepared in exactly the same manner except that partially saponified polyvinyl alcohol with a degree of saponification of 80 mol% (Poval 420 manufactured by Kuraray) and 1.0 part of a decomposable blowing agent was added, and the slurry was prepared using a whipping machine for confectionery production. After entraining enough air bubbles,
Polyethylene terephthalate film with glass mat (
It was laid on a bed of filament matte MF6OF manufactured by Nittobo.

Thereafter, it was immediately dried and heat-treated at 120° C. for 30 minutes.
The physical properties of the obtained sheet-like material are as shown in Table 4. Specific gravity is 0.
．． 18, it is highly flexible, has excellent heat insulation properties, and has excellent strength despite its light specific gravity, making it suitable for building interior materials (especially ceiling materials, etc.). Example 7 A continuous piece of vinylon cheesecloth (Cremona cheesecloth-300 manufactured by Kuraray) was passed through the slurry container prepared in Example 1-1, and the excess slurry attached to the cheesecloth was scraped off by sandwiching it between two rubber rollers. After making sure the thickness was uniform, it was dried by blowing hot air.

Claims (1)

[Claims] 1. A slurry containing as essential components an inorganic powder that does not harden by reaction with water and a thermoplastic resin emulsion, and containing other additives as necessary, is formed into a sheet. A method for manufacturing sheet-shaped architectural interior materials, which is characterized by forming, drying, and heat-treating. 2. The method for producing a sheet-like architectural interior material according to claim 1, wherein gypsum dihydrate is used as the inorganic powder that does not harden by reaction with water. 3. The method for producing a sheet-like architectural interior material according to claim 1, wherein a vinyl acetate polymer emulsion is used as the thermoplastic resin emulsion. 4. The sheet-shaped architectural interior according to claim 1, which uses dihydrate gypsum as the inorganic powder that does not harden by reaction with water, and uses a vinyl acetate polymer emulsion as the thermoplastic resin emulsion. Manufacturing method of wood.