JPH0355306B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a composite heat insulating material whose core material is a phenolic resin foam having excellent fire prevention properties, heat insulation properties, etc., and which is used in various industrial fields such as construction. [Prior Art] Conventionally, phenolic resin foam, which has excellent heat insulating properties, flame retardant properties, and fire retardant properties, has been used as a heat insulating material in construction and other industrial fields. Although phenolic resin foam has such excellent performance, it has weaknesses in physical performance such as strength and elasticity compared to other plastic foams. Composite with surface materials such as various inorganic sheets or flame-retardant organic sheets to increase
Furthermore, gypsum board, asbestos cement board,
It is put into practical use in a composite form with calcium silicate plates, metal plates, etc. In particular, composite heat insulating materials of phenolic resin foam and asbestos-containing inorganic sheets are most widely used. [Problems to be Solved by the Invention] However, the conventional composite insulation materials have the following problems with the face material composited with the phenolic resin foam, so it is still difficult to achieve insulation that is sufficiently satisfactory for practical use. The material is not available on the market. That is, among conventional facing materials, inorganic sheets containing glass fibers, inorganic sheets containing asbestos fibers, inorganic sheets containing inorganic materials such as aluminum hydroxide, flame-retardant cellulose paper, etc. are used as inorganic sheets or flame-retardant organic sheets. Inorganic sheets containing asbestos fibers do not sacrifice the fire resistance of phenolic resin foam.
Although asbestos fibers have suitable properties as surface materials, their use is currently prohibited in some countries as they are designated as a specified chemical substance and are subject to restrictions from the standpoint of pollution prevention and occupational health. Glass fiber-containing inorganic sheets do not sacrifice fire resistance, but due to the characteristics of glass fibers, they have poor workability (irritating the skin), have poor bending durability and are difficult to handle, and are difficult to use as surface materials. It has drawbacks such as poor reinforcing properties and high cost. Although inorganic sheets containing inorganic substances such as aluminum hydroxide are nonflammable,
The face material does not retain its shape during combustion, has no positive effect on fire protection, and has a weak reinforcing effect as a face material. Although organic sheets are mechanically improved over phenolic resin foams, they have a negative effect on fire resistance. Furthermore, the above-mentioned inorganic sheets and organic sheets have insufficient moisture-proofing and waterproofing properties, and there are problems such as a decrease in insulation performance due to moisture permeation of the insulation material after installation, and attempts to improve waterproofing and moisture-proofing properties. When a waterproof layer is applied to these inorganic or organic sheets, there are problems such as poor adhesion to the phenolic resin foam. As mentioned above, inorganic sheets and organic sheets used as surface materials for phenolic resin foams have insufficient fire protection, environmental hygiene problems (asbestos toxicity, skin irritation), and poor handling. However, there are problems in terms of economic efficiency (expensive), reinforcing properties as a face material, etc. In view of the above problems, it is an object of the present invention to achieve fire retardancy, economy, environmental hygiene, reinforcing properties as a surface material, moisture proofing, waterproofing, and phenolic resin foam without using asbestos fibers or expensive heat-resistant inorganic fibers. The object of the present invention is to provide a composite heat insulating material that has excellent properties such as adhesion to face materials. [Means for Solving the Problems] According to the present invention, (1) a phenolic resin foam is used as a core material, and calcium silicate, aluminum hydroxide powder, fibrous material, binder and/or other materials are coated on one or both sides of the core material. (2) A composite heat insulating material made by integrally bonding an inorganic sheet made of an additive and a moisture-proof/waterproof material on the surface of the inorganic sheet, and (2) a phenolic resin foam as a core material and calcium silicate and aluminum hydroxide on one side. An inorganic sheet consisting of powder, fibrous substances, binders and/or other additives, and on one side gypsum board, rock wool hard board, calcium silicate board, asbestos cement board, pulp cement board, metal board, plywood board, wood wool A composite heat insulating material is provided in which face materials selected from the group consisting of cement board, wood cement board, vinyl chloride sheet, nonwoven fabric, and paper are bonded and integrated. Hereinafter, the composite heat insulating material of the present invention will be explained in detail. Structure of Inorganic Sheet Calcium silicate and aluminum hydroxide are used together in the inorganic sheet of the present invention. Aluminum hydroxide is in the form of a fine powder, and by adding an appropriate fixing agent to form a floc, it can be entangled with fibers such as pulp and made into paper. The rate of entanglement decreases, leading to a decrease in papermaking yield. On the other hand, when calcium silicate is used in combination, aluminum hydroxide particles are entangled with calcium silicate aggregates, and the aggregates are made into fibrous material, resulting in a decrease in yield even at low basis weights. In addition, the resulting product has sufficient strength due to the strong bond between aluminum hydroxide, calcium silicate, and fibers. Aluminum hydroxide in the present invention is Al(OH) ₃
It is usually in the form of a white powder with a purity of 99% or more, and coarse particles impede the surface smoothness of the sheet and reduce the strength of the sheet, so the average particle size is 50μ or less. Preferably it is 15μ or less. The main component of calcium silicate in the present invention is CaO−
It is composed of SiO ₂ -H ₂ O and can be of any type, such as wollastonite group, tobermorite group, gairolite group, etc., as long as the molar ratio of CaO/SiO ₂ is in the range of 1:2 to 2:1. The shape may be any shape as long as it is needle-like, plate-like, thin-film-like, or a secondary aggregate thereof. For example, calcium silicate, which does not have the above-mentioned shape characteristics, such as C-S-H gel, is not used in the inorganic sheet in the present invention. The calcium silicate in the inorganic sheet of the present invention is primarily effective in binding aluminum hydroxide, so it is more preferable that the calcium silicate has acicular shape and/or secondary aggregates thereof. . When producing the inorganic sheet of the present invention using the above-mentioned calcium silicate as a raw material, the calcium silicate should be at least twice or more in terms of solid content weight ratio, especially 5
It is preferable that the water content is at least twice as high. If calcium silicate is excessively dehydrated by compression or heating, the effect of entangling aluminum hydroxide particles will be reduced even if paper is made by dispersing it in a large amount of water, resulting in a decrease in yield during paper making. The ratio of calcium silicate to aluminum hydroxide is in the range of 2:8 to 8:2 by weight. If the ratio of calcium silicate is too small, the resulting inorganic sheet will have high nonflammability, but the strength of the sheet will be insufficient, and the drainage property during paper making will be poor, resulting in a significant decrease in productivity, making it difficult to obtain the product of the present invention. I can't do it. On the other hand, if the ratio of aluminum hydroxide is too small, the self-extinguishing property, that is, the nonflammability will decrease, and the cost of raw materials for papermaking will increase. The total weight ratio of calcium silicate and aluminum hydroxide is required to be 40 to 95%. If it is less than 40% by weight, sufficient nonflammability will not be ensured, and if it exceeds 95% by weight, the fiber content will be relatively reduced and the properties as a sheet will be impaired. In view of both the physical properties and nonflammability of the sheet, it is particularly preferable that the total amount of calcium silicate and aluminum hydroxide is 55 to 85% by weight. In the present invention, the inorganic sheet consists of fibers and other additives other than the above-mentioned calcium silicate and aluminum hydroxide, and the total amount of these is required to be 5 to 60% by weight. A requirement is that the content of fibers and inorganic fibers be 5 to 30% by weight. The presence of organic fibers and inorganic fibers not only improves sheet formation, but also improves strength, flexibility, heat resistance,
It is essential for the composition of the inorganic sheet in the present invention because it contributes to ensuring properties such as flexibility and improving yield during papermaking, but when the fibers are organic fibers, as the ratio increases, the nonflammability decreases. . The range is therefore limited to 5-30% by weight. When organic fibers and inorganic fibers are blended alone, the blending ratio is determined from the viewpoint of sheet strength and nonflammability. Usually, a combination of organic fibers and inorganic fibers is suitable, but the blending ratio of inorganic fibers is preferably 0 to 10% by weight from the viewpoint of workability and folding durability. As organic fibers, cellulose fibers such as N-type or L-type kraft pulp, recycled pulp, etc., and various synthetic fibers can be used, but it is generally preferable to use cellulose fibers from the viewpoint of economical efficiency. Glass fibers, ceramic fibers, and rock wool can be used as inorganic fibers, but when rock wool and ceramic fibers are used, it is necessary to remove non-fibrous substances contained in these fibers, which is difficult to simplify the process. Therefore, it is appropriate to use glass fiber cut to 10 mm or less. Regarding the above formulations, organic binders, 0 to 30% by weight of inorganic fillers, fixing agents, sizing agents, colorants, etc.
Blend. The upper limit of 30% by weight is limited to maintain the nonflammability of the sheet. Organic binders include acrylic resin, vinylidene chloride resin, SBR,
Synthetic rubber such as NBR, ethylene vinyl acetate resin,
Examples include powders and emulsions of thermosetting resins such as phenolic resins. Inorganic fillers are used to reduce costs, and include calcium carbonate, gypsum, mica, silica sand, and talc. Typical examples of the fixing agent include sulfuric acid and polyacrylamide. As a sizing agent, glue,
Examples include alkyl ketene dimer, rosin size, and wax emulsion. As a coloring agent,
Commercially available organic/inorganic composite or inorganic pigments can be used. Manufacture of inorganic sheet To manufacture the inorganic sheet of the present invention, predetermined proportions of calcium silicate, aluminum hydroxide, fibrous substances, and other additives are added to a large amount of water with a solid content.
It can be obtained by uniformly dispersing it at a concentration of 0.5% or more and then making the paper using a conventional method using a paper machine such as a fourdrinier type (fourdrinier type), a cylinder type (oliver type), a funnel former type, or an inclined type. I can do it. The inorganic sheet manufactured here has a density of 0.4 or more, and the thickness is
It is 0.1mm or more. Surface treatment of inorganic sheet with moisture-proofing/waterproofing agent The inorganic sheet obtained by the above method can be integrated with phenolic resin foam and used as a composite heat insulating material. When used in materials, it is necessary to further provide waterproofness, moistureproofness, and heat ray reflection performance. In order to meet this purpose, it is effective to use a composite inorganic sheet laminated with a plastic film or nonwoven fabric, or a composite laminated inorganic sheet with aluminum foil or an aluminum vapor-deposited film. The selection criteria for plastic film or non-woven fabric depends on the thickness, but moisture resistance,
From the viewpoint of waterproofness, it is preferable to use one that is sparingly soluble in water and flame resistant. Films suitable for this purpose include, for example, thin PE film or PP film, thin to
Examples include PET film, polyamide film, PVC resin film, and vinylidene chloride resin film. For lamination with aluminum foil or aluminum vapor-deposited film, lamination processing can be carried out by transferring a metal aluminum expanded foil or a PET film or the like vapor-deposited aluminum onto the inorganic sheet. Furthermore, in order to improve the adhesion with the phenolic resin foam, an oxide film was formed on the composite inorganic sheet by corona discharge treatment.
Alternatively, it is preferable to perform a simp processing in which countless minute holes are made, or a combination of both methods. Phenol Resin Foam As the highly flame-retardant phenolic resin foam used in the present invention, any conventionally known type of phenolic resin foam can be used.
Specifically, it also contains powdered novolak type phenolic resin, liquid aqueous or non-aqueous resol type phenolic resin, urethane, epoxy, melamine, and urea-modified phenolic resin. An amine such as hexamethylenetetramine is added to the phenolic resin,
Contains a curing agent selected from inorganic acids such as phosphoric acid and hydrochloric acid, organic acids such as para-toluenesulfonic acid and phenolsulfonic acid, a foam stabilizer such as a silicone nonionic surfactant, and a foaming agent such as fluorocarbon. , a phenolic resin foam cured by heating and foaming can be mentioned. Manufacturing method of composite heat insulating board The inorganic sheet is bonded and integrated with the phenolic resin foam to finally take the form of a composite heat insulating material. An inorganic sheet is placed on the surface, and the inorganic sheet is injected or applied and foamed to harden to form an integrated structure.However, the resulting phenolic resin foam is then coated with a commercially available adhesive such as epoxy resin, vinyl acetate resin, or rubber-based resin, and then joined through post-processing. It is also possible to take a method of integration. Furthermore, on one side, gypsum board, rock wool hard board, calcium silicate board, asbestos cement board,
Pulp cement board, wood wool cement board, plywood board,
When using a metal plate, vinyl chloride sheet, nonwoven fabric, or paper, the same method as the above composite method can be used. The configuration of the composite heat insulating material of the present invention is illustrated in FIGS. 1 to 4. Fig. 1 shows a composite heat insulating material composed of an inorganic sheet 1 and a phenolic resin foam 3, Fig. 2 shows a composite heat insulating material composed of an inorganic sheet 1 - a phenolic resin foam 3 - an inorganic sheet 1, and Figs. The figure shows a composite heat insulating material consisting of an inorganic sheet 1, a phenolic resin foam 3, and a face material 2. In particular, FIG. 4 shows one embodiment of a composite heat insulating material in which the face material is a metal panel. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. (1) Production of composite insulation material 84 parts by weight of phenol, 558 parts by weight of 37% formalin, and 11.1 parts by weight of calcium hydroxide were charged into a flask, and 90 parts by weight of calcium hydroxide were charged. The reaction was carried out isothermally at ℃ for 60 minutes, then 85 parts by weight of brominated cresol monoglycidyl ether was added, and the reaction was continued for an additional 20 minutes. The liquid was neutralized and dehydrated under reduced pressure at 80°C to obtain a resol type phenolic resin liquid having a solid content of 89% by weight, a viscosity at 30°C of 57 poise, free phenol of 3.0% by weight, and free formalin of 1.9% by weight. To 100 parts by weight of this resin liquid, 20 parts by weight of trichloromonofluoromethane as a foaming agent, 0.2 parts by weight of a foam stabilizer (L-5340 manufactured by Union Carbide), 15 parts by weight of para-toluenesulfonic acid as a hardening agent, and additives ( Flame retardant) After blending 10 parts by weight of antimony trioxide and adding a PH adjuster so that the PH of the blend is neutral, this is mixed between an inorganic sheet and a face material having the following composition or an inorganic It was supplied between the sheet and the inorganic sheet and heated at 70°C for 20 minutes to foam and harden it. Alternatively, a phenolic resin foam separately molded into a plate shape was adhered to an inorganic sheet using an adhesive. [] (A) Phenol resin foam density: 42Kg/
m ³ , thickness: 16mm (B) Gypsum board: General commercial product (9mm thickness) (C) Inorganic sheet: The following Calcium silicate (xonotlite): Solid content concentration in slurry obtained by hydrothermal synthesis 5% by weight of calcium silicate. Most of the material was composed of fine needle-like crystals and secondary aggregates thereof, and X-ray diffraction revealed that most of the material was zonolite. Aluminum hydroxide: Purity 99.7% Average particle size 4 μ. (manufactured by Nippon Light Metal Co., Ltd.) Glass fiber: E glass Cut length 3 mm Pulp: LBKP/NBKP ratio 8/2, Canadian standard freeness beaten to 350 c.c. Fixing agent: Anionic - manufactured by Meisei Chemical Industry Co., Ltd.
Product Name Firex M Cationic - Manufactured by Meisei Chemical Industry Co., Ltd. Product Name Firex
RC107 Binder: Vinylidene chloride resin emulsion (approximately 40% concentration, manufactured by Kureha Chemical Co., Ltd.) The above raw materials were mixed with 33% calcium silicate, 30% pulp, 3% glass fiber, 30% aluminum hydroxide, 3% binder and Dispersed in water at a weight ratio of 1% fixative and at a concentration of about 1%,
Paper was made using a Fourdrinier paper machine and press-dried to obtain an inorganic sheet. The physical properties of the obtained inorganic sheet are as follows. Physical properties of inorganic sheet: Density…0.51, Thickness…0.27mm, Basis weight…138
g/m ² , tensile strength (vertical)...3.4Kg/15mm
Width, tensile strength (horizontal)…2.3Kg/15mm width,
Air permeability: 43 seconds, restricted oxygen index: 41, flame retardancy: Passed flame retardant class 1. <Measurement method> Tensile strength; JIS P 8113 Oxygen restriction index; JIS K 7201 Air permeability; JIS P 8117 Flame retardance; JIS A 1332 45° Mezkel burner method; heating time: 3 minutes [] (A) Phenol foam density: 58Kg/ ^m3 , thickness: 15mm (B) Calcium silicate board: General commercial product (10mm thickness) (C) Inorganic sheet: PE on the inorganic sheet
Laminated film (approximately 10μ thick), thickness: 0.28mm [] (A) Phenol foam density: 45Kg/mm ³ ,
Thickness: 13mm (B) Rock wool hard board: density 0.4, thickness 12
mm, semi-flammable (grade 2 flame retardant) type, manufactured by Nittobo Co., Ltd. Mineraboard (C) Inorganic sheet: Inorganic sheet with corona discharge and simp processing at 2 inch intervals, thickness: 0.28 mm [] ( A) Phenol resin foam density: 62Kg/
m ³ , thickness: 25mm (B) Inorganic sheet: 2 sheets laminated with aluminum vapor-deposited film (approx. 3μ thickness) on inorganic sheet [] (A) Phenol resin foam density: 55Kg/
^m3 , thickness: 20mm (B) Metal plate: Colored galvanized steel plate, thickness 0.45mm, polymer coated type (commercially available product) (C) Inorganic sheet: Aluminum vapor deposited film on inorganic sheet (approx. 3μ thick) PE (approx. 10μ (Thickness) sequentially laminated and subjected to corona discharge and simp processing, thickness: 0.29mm [] (A) Phenol resin foam density: 50Kg/
m ³ , thickness: 25mm (B) Inorganic sheet: 2 inorganic sheets [] (A) Phenol resin foam density: 57Kg/
m ³ , thickness: 25mm (B) Inorganic sheet: 1 piece of inorganic sheet _{No. 9} In the production of the above-mentioned composite insulation material, regarding its basic structure, [] to [] refer to Figure 3 [] and [] Figure 2, [] is the fourth
See Figure 1 for figures and []. (2) Performance of composite insulation material Composite insulation material manufactured as above [ ] ~
As a result of evaluating the adhesiveness between the inorganic sheet and the phenolic resin foam of [] by a peeling method, the adhesive strength showed a value of 0.2 to 0.4 Kg/cm, and the phenolic resin foam material adhered to the face material. Adhesion was good. Composite insulation materials [] to [] of the present invention and commercially available urethane resin foam (density 25 Kg/cm ³ , thickness
25mm) and the same inorganic sheet used in the composite insulation material [] was bonded and integrated with vinylidene chloride adhesive, and other characteristic values are shown in the following performance test result table. The bending strength was measured according to JIS A9514, the thermal conductivity was measured according to JIS A1413, and the fire resistance was measured by a quasi-nonflammability test according to Ministry of Construction Notification No. 1231.

【table】

[Table] [Effects of the Invention] As explained above, the composite insulation material of the present invention has extremely excellent performance such as fire retardancy, heat insulation, moisture proofing, and mechanical properties, and is used as a building material and as a material in various industrial fields. It is useful as Furthermore, the composite heat insulating material of the present invention is constructed as described in detail, and the foamed phenolic resin layer and the surface material plate are integrally molded, so that the resin layer and the surface material plate have excellent adhesion, so that the insulating heat and the surface material plate are excellent. Interior construction can be easily carried out and construction speed can be increased. Furthermore, since the foamed phenolic resin layer is flame retardant and does not emit smoke or harmful gases, it can exhibit excellent practical effects.

[Brief explanation of drawings]

1 to 4 are cross-sectional views of the composite heat insulating material of the present invention. 1...Inorganic sheet, 2... Face material, 3... Phenol resin foam.

Claims (1)

[Scope of Claims] 1. An inorganic sheet having a phenolic resin foam as a core material, and an inorganic sheet comprising calcium silicate, aluminum hydroxide powder, fibrous material, binder and/or other additives on one or both sides of the core, and optionally the inorganic sheet. A composite insulation material made by bonding moisture-proof and waterproof materials to the surface of the 2. The inorganic sheet contains (a) 40 to 95% by weight of calcium silicate and aluminum hydroxide powder in a weight ratio of 2:8 to 8:2, (b) organic fibers, glass fibers, ceramic fibers, and rock wool fibers. (c) 0 to 30% by weight of inorganic fibers selected from the group consisting of (c) binders and other additives, and the main component of the calcium silicate is CaO- _SiO
-H ₂ O, the molar ratio of CaO and SiO ₂ is in the range of 1:2 to 2:1, and the CaO-
Claim 1, which is an inorganic sheet made by dispersing a composition in water and making paper, in which the crystal shape of SiO ₂ -H ₂ O is needle-like, plate-like, thin film-like, or a secondary aggregate thereof. Composite insulation materials as described in section. 3. The composite heat insulating material according to claim 1, wherein the moisture-proof/water-proof material is a synthetic resin film or nonwoven fabric having moisture-proof and waterproof properties. 4. The composite heat insulating material according to claim 1, wherein the moisture-proof/waterproof material is an aluminum vapor-deposited film or foil. 5. The moisture-proof/waterproof material is a lamination of (a) a moisture-proof and waterproof synthetic resin film or nonwoven fabric and (b) an aluminum vapor-deposited film or foil in any order. Composite insulation. 6. The composite heat insulating material according to claim 1, wherein the inorganic sheet is an inorganic sheet subjected to corona discharge treatment, simp processing, or both. 7. Claims in which the moisture-proof/waterproof material is a synthetic resin film or nonwoven fabric, or an aluminum vapor-deposited film or foil, which has been subjected to corona discharge treatment, simp processing, or both, and has moisture-proof and waterproof properties. Composite heat insulating material according to item 1 or 5. 8 Phenol resin foam is used as the core material, and one side of it is coated with calcium silicate, aluminum hydroxide powder,
An inorganic sheet made of fibrous material, a binder and/or other additives, and on the other side gypsum board, rock wool hard board, calcium silicate board, asbestos cement board, pulp cement board, metal board, plywood board, wood wool cement board, A composite insulation material made by integrally bonding face materials selected from the group consisting of wood cement boards, vinyl chloride sheets, nonwoven fabrics, and paper. 9. The inorganic sheet is made of (a) 40 to 95% by weight of calcium silicate and aluminum hydroxide powder in a weight ratio of 2:8 to 8:2, (b) organic fibers, glass fibers, ceramic fibers, and rock wool fibers. 5 to 30% by weight of inorganic fibers selected from the group consisting of _:
-H ₂ O, the molar ratio of CaO and SiO ₂ is in the range of 1:2 to 2:1, and the CaO-
Claim 8, which is an inorganic sheet made by dispersing a composition in water and making paper, in which the crystal shape of SiO ₂ -H ₂ O is needle-like, plate-like, thin film-like, or a secondary aggregate thereof. Composite insulation materials as described in section.