JPH0455587B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a composite heat insulating material having fire prevention/insulation properties and moisture proof/waterproof properties that is used in various construction fields. [Prior Art] Phenol resin foam obtained by foaming and curing phenolic resin has excellent properties such as heat insulation, flame retardancy, and fire resistance, and is widely used as a heat insulating material in various construction fields. ing. However, as mentioned above, although the phenolic resin foam has excellent thermal insulation properties, it does not have sufficient mechanical properties such as strength and elasticity when compared to other resin foams. For this reason, for the purpose of reinforcing the mechanical properties and obtaining better fire prevention performance, for example, composites made of various inorganic sheets, flame-retardant organic sheets, etc. with skin materials are used. has been done. [Problems to be Solved by the Invention] By the way, the skin material in the composite of the conventional skin material made of an inorganic sheet or a flame-retardant organic sheet and a phenol resin foam is an inorganic sheet containing glass fiber or an inorganic sheet containing asbestos fiber. Inorganic sheets, such as inorganic sheets made of inorganic compounded sheets such as Al(OH) ₃ , and organic sheets made of flame-retardant cellulose paper, etc.; Although the properties are not sacrificed, the workability of glass fiber is poor, and the breakage resistance of the sheet itself is poor, resulting in poor handling properties.Furthermore, the reinforcing properties as a skin material are poor. Also, inorganic sheets containing asbestos fibers have the disadvantages that asbestos is a source of pollution and their use is restricted from the standpoint of occupational health and environment. Although inorganic compound sheets are satisfactory in terms of nonflammability, they do not have the ability to retain the shape of the skin material during combustion, and are not satisfactory in terms of improving fire resistance, and also have poor reinforcing performance as a skin material. Furthermore, organic sheets have insufficient flame retardancy, sacrificing the fire retardant properties of phenolic resin foam. Note that none of the above-mentioned skin materials have moisture-proof or waterproof properties, and if they are constructed using a direct pouring process in which mortar or the like is directly poured, not only do they not have waterproof properties against water intrusion, but they also have high When the construction is carried out in a humid atmosphere, the phenolic resin foam also has the disadvantage that the heat insulating performance of the phenolic resin foam is significantly lowered as a result of moisture penetrating into the phenolic resin foam after the construction. In addition, composite insulation materials that use a completely moisture-proof sheet as the skin material and directly foam and harden phenolic resin on the surface of the sheet can prevent moisture from entering from the outside, but moisture can be generated during molding of the phenolic resin foam. The water vapor produced by the blowing agent and the gas generated by the blowing agent remain within the phenolic resin foam, and the adhesive strength between the skin material and the phenolic resin foam decreases over time due to the influence of this water vapor, which reduces durability. Some composite insulation materials cannot be used. In contrast, the present invention eliminates all the drawbacks of the conventional composite heat insulating material made of a phenolic resin foam using a skin material, and moreover, the phenolic resin is directly foamed and cured on the skin material. Since the number of manufacturing steps is small, the manufacturing efficiency is high, and the high adhesive strength between the skin material and the phenolic resin foam reduces moisture and foaming that occurs during molding of the phenolic resin foam. Moisture-proof composite insulation that does not deteriorate due to gases caused by agents, has excellent and durable adhesive strength between the skin material and phenolic resin foam, and also has moisture-proof properties. It provides materials. [Means for Solving the Problems] The moisture-proof composite insulation material of the present invention is a phenolic resin with a skin material bonded and integrated on at least one side, which is obtained by directly foaming and curing a phenolic resin on the surface of the skin material. A composite heat insulating material made of foam, and the skin material is a composite sheet of any one of the following (a), (b), and (c). (a) A composite sheet consisting of a flame-retardant or noncombustible sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds, and a breathable synthetic resin film with perforations of 0.1 to 2 mm in diameter. (b) A composite sheet consisting of a flame-retardant or noncombustible sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds, and a breathable metal-deposited film or metal foil with perforations of 0.1 to 2 mm in diameter. (c) A flame-retardant or noncombustible sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds, and a synthetic resin film with perforations of 0.1 to 2 mm in diameter, as well as a synthetic resin film with perforations of 0.1 to 2 mm in diameter. A composite sheet made of a laminated sheet with a breathable metallized film or metal foil. In the moisture-proof composite insulation material of the present invention having the above structure, the above (a),
When the skin material made of composite sheet of either (b) or (c) is joined and integrated, the other side is usually plaster board, metal plate, asbestos cement board, etc. Calcium silicate board, pulp cement board, wood wool cement board, wood chip cement board, rock wool hard board, vinyl chloride sheet, non-woven fabric,
Paper, woven fabric, etc. are often used. Each component of the moisture-proof composite heat insulating material of the present invention will be explained below. Skin material The skin material used in the moisture-proof composite insulation material of the present invention is a flame retardant sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds, or a sheet that is both noncombustible and air permeable.
A breathable synthetic resin film with perforations of 0.1 to 2 mm, a breathable metal-deposited film or metal foil with perforations of 0.1 to 2 mm in diameter, or the above-mentioned breathable and waterproof synthetic resin film. Similarly, it is a composite sheet made of the above-mentioned breathable/waterproof metal vapor-deposited film or metal foil and a laminated sheet, that is, a laminated integrated sheet. Sheets with an oxygen index of 25 or higher and air permeability of 20 to 200 seconds Seats with an oxygen index of 25 or higher and air permeability of 20 to 200 seconds:
For example, N-type or L-type kraft pulp, cellulose fibers such as recycled pulp, organic fibers made of synthetic fibers such as polyethylene, nylon, polypropylene, bironin, glass fibers, rock wool, ceramic wool, calcium silicate fibers, sepiolite, attapulgite, potassium titanate. Inorganic fibers such as fibers (for rock wool and ceramic wool, non-fibrous materials are removed), inorganic or organic flame retardants such as aluminum hydroxide, antimony trioxide, gypsum, guanidine phosphate, ammonium polyphosphate, charcoal, mica Powder or emulsion type organic binder made of inorganic fillers such as silica sand and talc, thermoplastic resins such as acrylic resin, vinylidene chloride resin, SBR, NBR, ethylene/vinyl acetate resin, and thermosetting resins such as phenolic resin. A suspension containing a solid component such as material, fixing agent such as sulfuric acid, polyacrylamide, glue, alkyl ketene dimer, sizing agent such as rosin size, wax emulsion, and pigment such as carbon black is prepared using a fourdrinier method. It is easily obtained by paper making, dehydration, and drying using a general paper machine such as a circular mesh type, rotoformer, or inclined Fourdrinier type, and usually has a thickness of 0.1 to 0.5 mm and a density of 0.4 to 0.8. It is used as a skin material because it has a sufficient reinforcing effect. In addition, in the suspension containing the solid components (papermaking raw material), organic substances (organic fibers, organic binders,
60% of solid components (fixing agents, sizing agents, organic flame retardants)
When the oxygen index of the sheet obtained is less than % by weight,
25 or more, but if organic fiber is highly blended, it will be 10
More than % by weight of organic flame retardant is required. In addition, the total amount of organic binder and fixing agent used to improve the tensile strength of the resulting sheet is 10% by weight.
It should be kept below. On the other hand, if the inorganic fiber content is 10% by weight or more, the air permeability of the resulting sheet will be 200 seconds or less. Therefore, it is of course possible to easily obtain a sheet that satisfies the conditions of an oxygen index of 25 or more and an air permeability of 20 to 200 seconds by adjusting the solid components of the suspension. Breathable synthetic resin film The breathable synthetic resin film having a group of perforated holes with a hole diameter of 0.1 to 2 mm is preferably one that is poorly soluble in water and has flame resistance, such as polyethylene film, polypropylene film, polyethylene terephthalate film. , vinyl chloride film, vinylidene chloride film, polyamide film, etc., which have been subjected to perforation processing such as clothing processing, are used, but in the case of synthetic resin films made of nonpolar polymers, adhesiveness can be improved by corona discharge processing. Those that have been treated are preferably used. Breathable metal vapor deposited film or metal foil A breathable metal vapor deposited film having a group of perforated holes with a hole diameter of 0.1 to 2 mm is produced by forming an aluminum vapor deposited film on a synthetic resin film such as a polyethylene terephthalate film, and then perforating the film. What is provided will be used. The breathable metal foil having a group of perforated holes with a diameter of 0.1 to 2 mm is, for example, a foil obtained by expanding metal aluminum and perforated therein. Raw material for forming a phenolic resin film Conventionally known raw materials for forming a flame-retardant phenolic resin foam are used. in particular,
Powdered novolac type phenolic resin, liquid aqueous or non-aqueous resol type phenolic resin,
Phenol resins such as modified phenolic resins such as urethane, epoxy, melamine, and urea, amines such as hexamethylene and tetramine, inorganic acids such as phosphoric acid and hydrochloric acid, and organic acids such as paratoluenesulfonic acid and phenolsulfonic acid. A composition containing a curing agent selected from among, a flame retardant, a corrosion resistant agent, a foam stabilizer such as a silicone nonionic surfactant, a foaming agent such as fluorocarbon, etc. is used. [Example] The specific structure of the moisture-proof composite heat insulating material of the present invention will be described below based on manufacturing examples. Examples/Comparative Examples A phenolic resin foam having the same composition as described below is formed between the skin materials (1) and (2) by using the skin material (1) and the skin material (2) having the compositions described below. Moisture-proof composite insulation materials Example 1 and Example 2, which are example products of the present invention, are produced by directly supplying raw materials, heating them, and foaming and curing them.
Composite heat insulating materials Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were obtained as Example 3 and Comparative Example products. Skin material (a) 33% by weight of calcium silicate fiber, 30% by weight of pulp (NBKP, degree of beating 350), 3% by weight of glass fiber (E glass: cut length 3mm), 30% by weight of aluminum hydroxide (average particle size approximately 4μ) %, 1% by weight of fixing agent + sizing agent, and ³ % by weight of vinylidene chloride resin as solid components. Vertical) 4.2Kg/15mm width, oxygen index 39, air permeability 51 seconds sheet [1] and 10μ thick polyethylene film perforated with clothing (φ=0.2mm) at 5mm intervals for ventilation. This composite sheet is made by laminating a synthetic resin film [2] with a hot melt type adhesive applied to the surface of the synthetic resin film [2] so that the perforations in the synthetic resin film [2] will not be blocked. Skin material (b) A composite sheet in which the surface of the synthetic resin film of the skin material (a), which is made of a composite sheet of the sheet [1] and the synthetic resin film [2], is subjected to corona discharge machining. Skin material (c) Rock wool (removed shot type) 30% by weight,
A suspension containing 50% by weight of pulp (NBKP, freeness 350), 3% by weight of glass fiber, 3% by weight of vinylidene chloride resin, 13% by weight of antimony trioxide, and 1% by weight of fixing agent + sizing agent is produced. A sheet [3] with a basis weight of 150 g/m ² , thickness 0.29, tensile strength (vertical) 4.5 Kg/15 mm width, oxygen index 32, and air permeability 41 seconds obtained by dehydration and drying [3], and polyethylene terephthalate film ( A breathable metal vapor deposited film [4] in which a metal vapor deposited film with a thickness of 15 μ and an aluminum vapor deposited film of approximately 3 μ in thickness was subjected to perforation processing using a clothing cloth (φ = 0.2 mm) at 5 mm intervals. A composite sheet laminated with a hot melt type adhesive applied to the surface of the metal vapor deposited layer so that the perforations in the metal vapor deposited film [4] will not be blocked. Skin material (d) Basis weight 200g/m ² , thickness 0.31mm, tensile strength (vertical)
Commercially available kraft paper with a width of 9.3Kg/15mm, an oxygen index of 19, and an air permeability of 160 seconds. Skin material (c) Basis weight 215g/m ² , thickness 0.31mm, tensile strength (vertical)
10.1Kg/15mm width, lined kraft paper with an oxygen index of 19 and an air permeability of 270 seconds (the backing is coated with SBR latex 15g/ ^m2 ). Skin material (f) The same sheet as sheet [1] in the skin material (a). Skin material (g) The same sheet as sheet [3] in the skin material (c). Raw materials for forming phenolic resin foam: 84 g of phenol, 558 g of 37% formalin, and 11.1 g of calcium hydroxide were put into two synthesis flasks, and reacted isothermally at 90°C for 60 minutes. Then, 85 g of brominated cresol monoglycidyl ether was added, and then After reacting for 20 minutes, sulfuric acid was added so that the pH after the reaction was 7.0 to 7.3, the reaction solution was neutralized, and dehydrated at 80°C under reduced pressure to reduce the solid content to 89% by weight and the viscosity at 30°C. A resol type phenolic resin liquid having 57 poise, 3.0% by weight of free phenol, and 1.9% by weight of free formalin was obtained. Next, to 100 parts by weight of this resin liquid,
20 parts by weight of trichloromonofluoromethane as a foaming agent, foam stabilizer (Union Carbide product L-
5340) 0.2 parts by weight, 15 parts by weight of para-toluenesulfonic acid as a curing agent, 10 parts by weight of antimony trioxide as an additive (flame retardant), and a PH adjuster to make the PH of the mixture neutral. added. The types of skin materials used in each of the Examples and Comparative Examples and the various physical property values of the resulting composite heat insulating materials are shown in a table. In each of the moisture-proof composite insulation materials in Examples 1 and 2, the skin material and the phenolic resin foam are integrated in such a way that the synthetic resin film surface of each skin material is in contact with the phenolic resin foam surface. The moisture-proof composite insulation material in Example 3 is one in which the skin material and the phenolic resin foam are integrated so that the sheet [3] surface of the skin material is in contact with the phenolic resin foam surface. .

[Front] Nera board
The physical properties of the composite heat insulating material were obtained using the following recipe. Adhesion...Evaluation by 180 degree peeling method. Thermal conductivity...JIS A1413 method. Bending strength...JIS A9514 method Fire resistance...Ministry of Construction Notification No. 1231 (JIS A1321)
Law. Waterproofness: Place a glass cylinder with a diameter of 5 cm on a composite insulation material, seal the area around the cylinder and the composite insulation material with a sealant, and waterproof it at a water column of 30 cm.
The degree of water penetration after being left in the sun was visually evaluated. Moisture permeability: 400 g of calcium chloride (desiccant) is placed at the bottom of a two-stage desiccator with a bottom diameter of 250 mm and a top diameter of 300 mm, a composite insulation material is placed on top, and the surrounding area is sealed with beeswax.
Leave it in a constant temperature and humidity chamber at ℃ and 50%RH for one week.
Moisture permeability was evaluated based on changes in the weight of calcium chloride (according to ASTM C-355). [Operations and Effects of the Invention] The moisture-proof composite heat insulating material of the present invention is made of a phenolic resin foam that is obtained by directly foaming and curing a phenolic resin on the surface of the skin and has a skin material bonded and integrated on at least one side. In the composite insulation material, the skin material has (a) an oxygen index of 25 or more and an air permeability of 20 to 200;
Second flame retardant or non-combustible sheet and pore size 0.1~2mm
or (b) a flame-retardant or noncombustible sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds and perforations with a hole diameter of 0.1 to 2 mm. Composite sheet with processed breathable metallized film or metal foil, or (c) Oxygen index 25 or higher, air permeability 20
~200 seconds flame retardant or non-combustible sheet and pore size 0.1~
Comprised of a composite sheet consisting of a breathable and waterproof synthetic resin film with 2 mm perforations and a laminated sheet with breathable metal-deposited film or metal foil, which also has 0.1 to 2 mm perforations. This is what has been done. Therefore, in the moisture-proof composite insulation material of the present invention,
The water vapor generated during foaming of the phenolic resin and the gas generated by the foaming agent penetrate through the skin material made of the composite sheet that is bonded and integrated with at least one side of the phenolic resin foam and are dissipated. There is no stagnation, and excellent permanent adhesive strength is achieved between the phenolic resin foam and the skin material. In addition, if the diameter of the perforated holes in the breathable synthetic resin film, metallized film, metal foil, etc. in the composite sheet used as the skin material is less than 0.1 mm, water vapor generated during foaming of the phenolic resin The effect of the gas generated by the blowing agent or foaming agent penetrating the skin material and dissipating becomes insufficient. In addition, in the moisture-proof composite insulation material of the present invention, a flame-retardant or noncombustible sheet with an air permeability of 20 to 200 seconds is incorporated into the skin material, so the phenol resin is foamed and hardened on the surface of the skin material. At this stage, a skin layer is formed on the surface of the phenolic resin foam, and at the same time, the phenolic skin layer bites into the sheet in contact with the phenolic resin foam in the composite sheet that is the skin material, making the sheet airtight. This is a composite insulation material that is completely moisture-proof and waterproof. In addition, if the diameter of the perforated holes in the breathable synthetic resin film, metallized film, metal foil, etc. in the composite sheet used as the skin material exceeds 2 mm, the formation of the skin layer may not be complete. There is a risk that moisture-proof and waterproof properties will not be obtained. Therefore, even when the composite heat insulating material of the present invention is constructed using a direct pouring method in which mortar or the like is directly cast, there is no risk of moisture intrusion, and the composite heat insulating material can be constructed in a high humidity atmosphere. Even in cases where moisture does not infiltrate, there is no possibility that the adhesive strength between the skin material and the phenolic resin foam will decrease, and there is no risk of deterioration in insulation performance due to moisture absorption. It has the following functions and effects.

Claims (1)

[Scope of Claims] 1. In a moisture-proof composite insulation material made of a phenolic resin foam obtained by directly foaming and curing a phenolic resin on the skin material surface and having a skin material bonded and integrated on at least one side, the skin material A moisture-proof composite insulation material, characterized in that is a composite sheet of any one of the following (a), (b), and (c). (a) A composite sheet consisting of a flame-retardant or noncombustible sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds, and a breathable synthetic resin film with perforations of 0.1 to 2 mm in diameter. (b) A composite sheet consisting of a flame-retardant or noncombustible sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds, and a breathable metal-deposited film or metal foil with perforations of 0.1 to 2 mm in diameter. (c) A flame-retardant or noncombustible sheet with an oxygen index of 25 or more and an air permeability of 20 to 200 seconds, and a breathable synthetic resin film with perforations of 0.1 to 2 mm in diameter, as well as perforations with a pore diameter of 0.1 to 2 mm. A composite sheet made of a laminated sheet with a processed breathable metallized film or metal foil.