JPH0740489A - Manufacture of inorganic composite molding - Google Patents

Abstract

PURPOSE:To provide a method for manufacturing reasonably a composite panel wherein durability and workability are excellent concerning the method for manufacture of the composite panel used for building materials such as wall material, roofing material, flooring material, etc., and fracture toughness required especially as the flooring material is improved. CONSTITUTION:(a) Bundled inorganic fiber and (b) solid composition at ordinary temperature of inorganic bulk material and thermosetting resin are in regular sequence or alternately scattered on an upper surface of inorganic fiber fabric or nonwoven fabric in a humid condition which is impregnated with a liquid thermosetting resin, and the composition is made to slip down and dispersed in gaps among the inorganic fiber bundle. The inorganic fabric or nonwoven fabric, inorganic fiber, and inorganic bulk material are bonded to be integrated with the thermosetting resin. In that case a portion of the thermosetting resin is preferably permeated in a state having a concentration gradient of resin from a lower part of the inorganic fiber layer to its upper part.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a composite panel used for wall materials, roof materials, floor materials and the like.

[0002]

2. Description of the Related Art Generally, plate-shaped panels used for walls and floors of buildings are excellent in fire resistance, dimensional stability, lightness and workability, and physical properties include fatigue resistance and impact resistance. However, the existing asbestos silica plate, fiber reinforced cement plate, wood, plastics, etc. all have advantages and disadvantages. As an inorganic composite molded article having these various properties, for example, Japanese Patent Publication No. 59-13473 discloses a lightweight molded article composed of a core layer mainly composed of pumice and a surface layer reinforced with inorganic fibers. 4-296552 discloses a composite panel in which a fiber sheet, a net and a cloth are adhered to improve fracture toughness. In this case, the resin is impregnated in advance and the solvent is removed to form a prepreg, and a panel having a dense structure suitable as an inorganic building material is provided.
That is, in general, when overlaying a fiber woven fabric impregnated with a thermosetting resin, a volatile matter such as a solvent or water may remain between the woven fabric and the base material, which may cause swelling or rupture. In many cases, volatile components are scattered and used as a prepreg.

[0003]

However, the molded articles obtained by these conventional techniques show good performances such as light weight, fire resistance, toughness, workability, etc., but their strength is not sufficient yet. Moreover, there is still room for improvement in the manufacturing method. In particular, in order to manufacture an inorganic building material having a dense structure by using a fiber sheet or the like, a prepreg forming step of scattering a solvent is generally required, and thus the step is complicated. It is an object of the present invention to improve this point and to provide a method for rationally producing a composite panel which is excellent in durability and workability and in particular has improved fracture toughness required as a flooring material. is there.

[0004]

Means for Solving the Problems That is, the present invention provides a wet inorganic fiber woven fabric or a non-woven fabric impregnated with a liquid thermosetting resin, (a) a focused inorganic fiber,
(b) A composition comprising an inorganic powder and a thermosetting resin that is solid at room temperature is sequentially or alternately sprayed, and the composition is slid and dispersed in the gaps of the inorganic fiber bundle, and the inorganic fiber woven fabric is thermally cured. Alternatively, the present invention provides a method for producing an inorganic composite molded article, which comprises integrally bonding a nonwoven fabric, an inorganic fiber and an inorganic powder material with a thermosetting resin. In this case, on the upper surface of the inorganic fiber woven fabric or non-woven fabric in a wet state impregnated with an excess amount of liquid thermosetting resin, a bundle of inorganic fibers is dispersed to form an inorganic fiber layer. It is advisable to infiltrate the part from the lower part to the upper part of the inorganic fiber layer in a state having a resin concentration gradient. Further, on the upper surface of the inorganic fiber woven fabric or nonwoven fabric in a wet state impregnated with a liquid thermosetting resin, (a) a bundle of inorganic fibers, (b) at a room temperature consisting of inorganic powder and thermosetting resin A solid composition is sprayed in order or alternately, the composition is slidably dispersed in the gaps of the inorganic fiber bundle to form one surface layer, and an inorganic lightweight aggregate having an average particle size of 1 mm or more is formed on the surface layer. A solid composition composed of an inorganic powder having an average particle diameter of 0.5 mm or less and a thermosetting resin is dispersed to form a core layer, and the core layer is formed on the core layer;
(a) a bundle of inorganic fibers, (b) an inorganic powder and a thermosetting resin, which are solid compositions at room temperature are sprayed sequentially or alternately, and the composition is slid and dispersed in the gaps of the inorganic fiber bundles. To form the other surface layer, heat-cure them, and bond them together to obtain an inorganic composite molded article having a layered structure.

The present invention will be described in detail below. First, place the inorganic fiber woven fabric or non-woven fabric on the release sheet or in the mold, and supply the thermosetting resin aqueous solution, solution (other than water) or emulsion liquid to the surface, Permeate into. The supply of the resin liquid can be performed by using a known device such as a spray device or a slot orifice coater, or by simply pouring the resin liquid onto the fiber fabric and leveling it with a brush or a spatula.

As the inorganic fiber woven fabric and non-woven fabric, cloth, net, sheet, mat-shaped woven fabric and non-woven fabric made of glass fiber, carbon fiber, ceramic fiber and the like can be used. Further, the thermosetting resin is a phenol resin,
Any general-purpose resin such as a urea resin, a melamine resin, an epoxy resin, or an unsaturated polyester resin may be used as long as an aqueous solution, a solution or an emulsion liquid can be prepared.

The mixing ratio of the thermosetting resin is 100 in the fiber woven fabric.
It is used in the range of 50 to 300 parts by weight in terms of solid content with respect to parts by weight, but since the amount of resin impregnated in the fiber woven fabric is usually about 50 to 100 parts by weight, excess resin is distributed on the woven fabric. It will be in the state of being. When the resin blending ratio is 50 parts by weight or less, the resin does not sufficiently reach the inside of the fiber bundle, resulting in insufficient strength development. Further, if it exceeds 300 parts by weight, the resin flows out and the thickness of the resin layer cannot be adjusted.

[0008] Next, while the impregnated and coated thermosetting resin is not dried and is in a wet state, the inorganic fiber woven fabric is sprinkled and laminated with a focused inorganic fiber having a length of at least 10 mm or more. The sprinkled fibers have a bulky matte shape, and part of the thermosetting resin penetrates into the inorganic fibers in contact with the woven fabric. At this time, when an excessive amount of thermosetting resin is present, the amount of resin that permeates the inorganic fiber layer is also large, the lower layer near the inorganic fiber fabric has a higher resin concentration, and the upper layer has a lower resin concentration. A concentration gradient is formed.

If necessary, a compression operation may be added to adjust the fiber bundle gap amount and the resin permeation amount.

As the bundled inorganic fibers, rovings and chopped strands composed of glass fibers, carbon fibers, ceramic fibers, etc. are used. From the viewpoint of workability and economy, the glass fiber rovings are cut to a predetermined length with an appropriate cutter device. It is desirable to use while cutting. Glass fiber roving is 5-25 μm monofilament 50
Approximately 250 strands are aligned, a binder is added to make one strand, and 10 to 30 strands are used as a base.

Next, on the above-mentioned inorganic fiber layer, a solid composition of an inorganic powdery material having an average particle size of 0.5 mm or less and a thermosetting resin is sprayed at room temperature to form a gap between the inorganic fiber bundles. Disperse by sliding down. At this time, the dispersion may be promoted by applying an operation such as vibration or compression after the application of the composition. By a series of these operations, a layered product composed of the inorganic fiber, the inorganic powder and the thermosetting resin is formed on the inorganic fiber woven fabric impregnated with the thermosetting resin.

The layered product obtained in this manner has, in addition to the concentration gradient of the resin described above, also between the inorganic powder and the fiber,
The lower layer near the inorganic woven fabric is richer in fibers, and the upper layer is richer in the inorganic powder and granular structure.

The inorganic powder is used as resin concrete or thermosetting resin filler, for example, natural sand such as river sand, sea sand, mountain sand, beach sand, silica sand, shelf sand, marble, granite, limestone, silica stone, Peridotite, andesite, crushed stones such as calcium carbonate, artificial bone agents, cement, gypsum, crushed granular materials such as glass, ceramics, shells, pigments such as alumina and red iron oxide, porous particles such as glass balloons, fly ash and perlite. Etc. can be used alone or in combination. In order to impart machinability to the obtained product, it is desirable to use it as a particle system containing porous particles such as glass balloons, fly ash and perlite. The average grain size is set to 0.5 mm or less because the dispersibility in the interstices of the inorganic fiber bundles deteriorates as the average grain size increases.

The blending ratio of the thermosetting resin is slightly different depending on the type of the inorganic powder or granules used and the type of the resin, and should be set according to each individual case. From the viewpoint of required performance and economical efficiency, the inorganic powder is used. 2 parts of thermosetting resin to 100 parts by weight
The range of ˜30 parts by weight is preferred. Further, additives such as a water repellent and a lubricant can be blended as necessary.

By heat-curing the mat-like composition obtained in the above forming step, an inorganic composite molded article according to one embodiment of the present invention can be obtained. Generally, the heat-pressure curing conditions are appropriately selected within a range of a press pressure of 1 to 50 kg, a heating temperature of 120 to 200 ° C., and a heating time of 5 to 60 minutes.

The inorganic molded body thus obtained is
The characteristics at the time of molding described above remain. That is, (1) a fiber woven fabric or a non-woven fabric impregnated with a thermosetting resin is arranged in the lowermost layer of the molded body, and is integrally bonded to the upper layer thereof. (2) The upper layer of the fiber woven fabric is composed of bundled inorganic fibers dispersed in the inorganic powder and granules, both of which are bonded by the thermosetting resin. (3) In the vicinity of the inorganic woven fabric, the composition is rich in resin and rich in bundled fibers, and therefore, the resin concentration is reduced, and the composition is rich in inorganic powder and granules.

Further, the above-mentioned layered product is used as one surface layer, and an inorganic lightweight aggregate having an average particle size of 1 mm or more, an inorganic powdery particle having an average particle size of 0.5 mm or less, and a thermosetting resin are formed on the surface layer. A core-layer is formed by spreading a composition that is solid at room temperature to form a core layer, and a focused inorganic fiber having a length of 10 mm or more, and an average particle size of 0.5 mm.
At room temperature, a solid composition of the following inorganic powder and thermosetting resin is sequentially or alternately sprayed to form another surface layer in which the composition is slid and dispersed in the interstices of the inorganic fiber bundles. It is also possible to form an inorganic composite molded body having a layered structure in which these are thermoset and bonded and integrated.

As the inorganic lightweight aggregate, natural and artificial lightweight aggregates such as volcanic pebbles, anti-fire stones, pearlite and expanded shale particles are used. The above-mentioned inorganic powder is used. The average particle size of the lightweight aggregate is set to 1 mm or more because the smaller the average particle size is, the heavier the weight of the obtained product becomes.
In addition, a combination with an inorganic powder or granular material having an average particle diameter of 0.5 mm or less results in a structure with large voids, which leads to an increase in the amount of resin used.

[0019]

EXAMPLES Examples of the present invention will be shown below. [Example 1] 200 g / m ^{2 of} basis weight on the release sheet
Plain weave glass cloth (KS-2200 manufactured by Kanebo Co., Ltd.) is placed on the surface, and a 60% solid content resol-based phenol resin aqueous solution (RG-600 manufactured by Asahi Organic Materials Co., Ltd.) 3
00 g / m ² was sprayed and impregnated. Next, 600 g / m ^{2 of} chopped strands prepared by cutting glass rovings (RS-240PR-348CS, manufactured by Nitto Boseki Co., Ltd.) into 40 mm are sprinkled and laminated thereon. Furthermore, 88 parts by weight of coarse-grain fly ash having a Blaine value of 1,500 cm ² / g (manufactured by Hokuden Kogyo Co., Ltd.) and 15% by weight of hexamethylenetetramine, a novolac type phenol resin (NH-70).
01, manufactured by Nippon Steel Chemical Co., Ltd.) 2,480 kg / m ² of a composition obtained by uniformly mixing 12 parts by weight of the composition was sprayed to form a mat-like composition in which the chopped strand gap was filled with the fly ash / resin composition. This composition is inserted into a hot press and pressed at a temperature of 160 ° C. and an initial pressure of 20 kg / m ² for 10 minutes to obtain an inorganic composite molded body.

The thus obtained composite molded article has the following properties when subjected to a bending test with the glass cloth surface facing down. Thickness 2.5 mm Density 1.25 g / cm ³ Flexural strength 1109 kgf / cm ² Flexural modulus 1000 kgf / mm ²

Example 2 The matte composition of Example 1 (state before thermosetting) is used as the lower surface layer. On the lower surface layer thereof, a particle density of 0.5 g / cm ³ and a particle size of 0.5 to 4.
A composition in which 44 parts by weight of 0 mm volcanic pebbles (manufactured by Omaru Industry Co., Ltd.), 50 parts by weight of the coarse-grained fly ash and 6 parts by weight of the above-mentioned phenol resin are uniformly mixed 15,480 g /
Disperse mm ² to form the core layer. Next, as an upper surface layer, a composition 4,200 composed of 200 g / m ^{2 of} chopped strands used in the lower surface layer, 82 parts by weight of coarse fly ash and 18 parts by weight of a phenol resin.
0 kg / m ² is sprayed in this order, the gap between the chopped strands is filled with the fly ash / resin composition, and a layer in which excess fly ash / resin composition is arranged is formed on the strand. Insert this laminate into a hot press and set the temperature to 1
Tighten for 25 minutes at 60 ° C and an initial pressure of 20 kg / cm ² ,
An inorganic composite laminated body having a sandwich structure in which one surface layer is reinforced with glass cloth is obtained.

The composite molded body thus obtained has the following properties. Thickness 25 mm Density 0.95 g / cm ³ Flexural strength 295 kgf / cm ² Flexural modulus 760 kgf / mm ²

[Comparative Example 1] The same as in Example 1, except that the glass cloth shown in Example 1 was impregnated with the resol-type phenolic resin in an amount of 33% by weight and then dried to form a prepreg. The chopped strands and the coarse-grained fly ash / phenolic resin composition are sprinkled and hot pressed under the conditions to obtain an inorganic composite molded body.

The composite molded body thus obtained has the following properties. Thickness 2.5 mm Density 1.25 g / cm ³ Flexural strength 835 kgf / cm ² Flexural modulus 790 kgf / mm ²

[0025]

EFFECTS OF THE INVENTION The composition of the present invention containing a relatively large amount of inorganic powder and thermosetting resin forms a structure having large voids, and a part of the voids can be formed by thermocompression molding. Remain and become a porous structure. Therefore, even if the fiber woven fabric or the non-woven fabric in a state where water or solvent remains is integrally thermocompression-molded, excess water or solvent can evaporate through this void in the hot-pressing process, so that water or solvent remains. It has become possible to directly composite-integrate existing fiber fabrics with this composition. Generally, when overlaying a fiber woven fabric impregnated with a thermosetting resin, volatile components such as solvent and water may remain between the woven fabric and the substrate, causing swelling or rupture. In many cases, the prepreg is used as a prepreg. However, in the present invention, the step of forming a prepreg for scattering the solvent is omitted, and the composite panel can be manufactured in an economical and labor-saving process. Further, a part of the thermosetting resin impregnated in the textile fabric permeates into the inorganic fibers and the inorganic powder particles in the vicinity of the fabric during the laminating operation or the hot pressing operation, and these inorganic fibers and the inorganic powder particles are infiltrated. It also contributes to the strengthening of the layer and greatly improves the physical properties. Also, the adhesion to the fiber woven fabric becomes good. Further, by using the wet fabric, the fabric can be placed smoothly on the release sheet, and it becomes easy to maintain the uniformity of the powder composition sprinkled on the release fabric. The operation becomes simpler. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a composite panel which is excellent in fire resistance, dimensional stability, economical efficiency, and workability, and moreover has improved fracture toughness which is particularly required as a flooring material. The effect is truly remarkable.

Claims (3)

[Claims] 1. A wet inorganic fiber woven fabric or a non-woven fabric impregnated with a liquid thermosetting resin is provided with (a) a bundle of inorganic fibers, (b) an inorganic powder and a thermosetting resin. The composition which is solid at room temperature is sprayed in sequence or alternately, and the composition is slidably dispersed in the gaps of the inorganic fiber bundle, and the inorganic fiber woven fabric or nonwoven fabric, the inorganic fiber and the inorganic powder are thermally cured. A method for producing an inorganic composite molded article, which comprises integrally bonding with a resin. 2. A thermosetting resin, wherein a bundle of inorganic fibers is sprinkled to form an inorganic fiber layer on the upper surface of a wet inorganic fiber woven fabric or nonwoven fabric impregnated with an excess amount of a liquid thermosetting resin. 2. The method for producing an inorganic composite molded article according to claim 1, wherein a part of the above is permeated from the lower part to the upper part of the inorganic fiber layer in a state having a resin concentration gradient. 3. A wet inorganic fiber woven fabric or non-woven fabric impregnated with a liquid thermosetting resin is provided on the upper surface of (a) a bundle of inorganic fibers, (b) an inorganic powder and a thermosetting resin. The composition which is solid at room temperature is sprayed sequentially or alternately, and the composition is slidably dispersed in the gaps of the inorganic fiber bundle to form one surface layer, and the inorganic material having an average particle diameter of 1 mm or more is formed on the surface layer. Lightweight aggregate,
A solid composition composed of an inorganic powder having an average particle size of 0.5 mm or less and a thermosetting resin is dispersed at room temperature to form a core layer, and (a) a focused inorganic fiber is formed on the core layer. , (B) The composition of the inorganic powder and the thermosetting resin, which is solid at room temperature, is sprayed in order or alternately, and the composition is slid and dispersed in the interstices of the inorganic fiber bundle to form the other surface layer. A method for producing an inorganic composite laminate molded article, which comprises heat-curing and bonding and integrating them to obtain an inorganic composite molded article having a layered structure.