JPH05169580A - Composite heat insulating material - Google Patents

Abstract

PURPOSE:To provide a composite heat insulating material obtained by integrally bonding a phenol resin foam and a non-combustible sheet containing no inorg. powder, excellent in the adhesiveness to phenol resin foam and excellent in various capacities such as fireproofness, environmental sanitation, moistureproofness, waterproofness or the like. CONSTITUTION:A non-combustible sheet composed of phosphate pulp and, if desired, a composite heat insulating material wherein a moistureproof and waterproof material is integrally bonded to the surface of the non-combustible sheet are bonded to the single surface or both surfaces of phenol resin foam 3 being a core material or the non-combustible sheet composed of phosphate pulp is bonded to the single surface of the phenol resin foam 3 being the core material and a base material selected from a group consisting of a gypsum board, a rock wool hard panel, a calcium silicate panel, an asbestos-cement board, a pulp-cement panel, a metal plate, veneer, a cemented excelsior board a cement chip board, a vinyl chloride sheet, a nonwoven fabric and paper are integrally bonded to the other surface of the phenol resin foam.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite heat insulating material having a phenol resin foam as a core material, which has excellent fireproof and heat insulating properties and is used in various industrial fields such as construction.

[0002]

2. Description of the Related Art Conventionally, as a heat insulating material, a phenol resin foam excellent in heat insulating property, flame retardant and fire resistant has been used in construction and other industrial fields. Phenolic resin foams have such excellent performances, but are weaker in adhesiveness to face materials than other plastic foams, and have weaknesses in physical performance such as strength and elasticity. In order to compensate for the weaknesses of such performance, and to further enhance the fireproof property, composites with face materials such as various inorganic sheets or flame-retardant organic sheets, further, gypsum board, asbestos cement board, calcium silicate board, It is put to practical use in a form combined with a metal plate and the like. In particular, the composite heat insulating material of phenol resin foam-asbestos blended inorganic sheet is most widely put to practical use.

[0003]

However, since the conventional face material composited with the phenolic resin foam has the following problems, the heat insulating material which is still practically sufficiently satisfactory is not provided to the market. Not not. First, as an inorganic sheet, an inorganic sheet mixed with asbestos fibers or an inorganic sheet mixed with an inorganic powder such as aluminum hydroxide or calcium carbonate has been used as a face material, and as an organic sheet, flame retardant impregnated. Organic sheets such as treated paper are used as face materials. Although the inorganic sheet containing asbestos fibers has suitable performance as a face material without sacrificing the fire resistance of phenol resin foam, asbestos fibers are specified as a specific chemical substance, and from the viewpoint of pollution prevention and occupational environment hygiene. Subject to use restrictions,
The use is currently prohibited in some countries. An inorganic sheet containing an inorganic powder such as aluminum hydroxide or calcium carbonate is non-combustible, but has no shape-retaining property of the face material during combustion and has no positive effect on fire resistance. In particular, the inorganic powder has a weak reinforcing effect as a face material because it has poor adhesion to the phenol resin foam. The flame-retardant treated organic sheet impregnated with the flame retardant improves phenol resin foam in terms of physical performance, but since the flame retardant is mixed with the pulp, it deteriorates and discolors the pulp, or is in use. The fire resistance is negative because the flame retardancy decreases or disappears when it gets wet with water. Furthermore,
The inorganic sheet and the organic sheet have problems such as insufficient moisture resistance and waterproofness, and deterioration of heat insulating performance due to moisture permeation of the heat insulating material after construction. As mentioned above,
Inorganic and organic sheets that have been conventionally used as a surface material for phenol resin foams have insufficient fire resistance, environmental hygiene problems (asbestos toxicity, skin irritation), and adhesion with phenol resin foams. Inferiority, poor handling, economy (expensive),
There is a problem in terms of reinforcement as a face material.

In view of the above problems, an object of the present invention is to provide a non-combustible material which does not contain inorganic powder and has excellent adhesiveness to phenol resin foam and excellent performances such as fire resistance, environmental hygiene, moisture resistance and waterproofness. It is an object to provide a composite heat insulating material in which a sheet and a phenol resin foam are joined and integrated.

[0005]

According to the present invention, there is provided (1) a composite heat insulating material comprising a phenol resin foam as a core material, and one or both surfaces of which are bonded and integrated with a non-combustible sheet of phosphorylated pulp. (2) Phenolic resin foam as a core material, one side or both sides of which is joined with a non-combustible sheet made of phosphorylated pulp,
Furthermore, a composite heat insulating material obtained by integrally bonding a moisture-proof and waterproof material to the surface of the non-combustible sheet. (3) Phenolic resin foam as a core material, one side of which is joined with a non-combustible sheet made of phosphorylated pulp, and the other side is bonded to gypsum board, rock wool hard board, calcium silicate board, asbestos cement board, pulp cement board, metal A composite heat insulating material obtained by joining and integrating base materials selected from the group consisting of a board, a veneer board, a wood wool cement board, a wood chip cement board, a vinyl chloride sheet, a non-woven fabric and paper. Although the non-combustible sheet used in the present invention contains phosphorylated pulp as an essential component, it may optionally contain a fiber substance, a binder and / or other additives. Hereinafter, the composite heat insulating material of the present invention will be described in detail.

Composition of non-combustible sheet: The non-combustible sheet of the present invention is obtained by a papermaking method in which phosphorylated pulp is an essential component and, if desired, a component containing a fibrous substance, a binder and / or other additives are dispersed in water to make paper. Be done. Phosphorylated pulp, which is an essential component, is a chemical combination of cellulose and ammonium phosphate.

[Chemical 1] It has the chemical formula: The amount of phosphorylated pulp used in the non-combustible sheet of the present invention is 30 to 100% by weight. 30% by weight
If it is less, the shape retention of the face material during combustion is insufficient. Examples of the inorganic fiber to be blended as desired include glass fiber, ceramic fiber, rock wool fiber and the like. The content of the inorganic fiber is 70% by weight or less. If it exceeds 70% by weight, the folding resistance of the noncombustible sheet and workability such as irritating the skin are deteriorated.

Regarding the above-mentioned composition, paper strength such as tensile strength when wet, papermaking retention improvement (retention) of the solid composition,
Organic fibers, organic binders, fixing agents, sizing agents, colorants and the like are added in a total amount of 30% by weight or less for the purpose of improving paper-making properties (water-repellency), imparting water repellency to sheets, coloring and the like. The upper limit of 30% by weight is limited to maintain nonflammability. Examples of the organic fibers include cellulose fibers such as N-type or L-type kraft pulp and recycled pulp, and various synthetic fibers.

Examples of the organic binder include acrylic resin, vinylidene chloride resin, synthetic rubber such as SBR and NBR, powder of thermosetting resin such as ethylene vinyl acetate resin and phenol resin, and emulsion. Representative examples of the fixing agent include a sulfuric acid band and polyacrylamide.
As a sizing agent, glue, alkyl ketene dimer,
Examples include rosin size and wax emulsion. As the colorant, organic, inorganic composite or inorganic general commercially available pigments can be used.

Manufacture of non-combustible sheet: The non-combustible sheet of the present invention is manufactured by uniformly mixing a predetermined proportion of phosphorylated pulp, fiber material, binder and other additives in a large amount of water at a solid content of 0.5% by weight or more. Long wire type (Ford linear type)
Circle net type (Oliver type), funnel former type,
Using an inclined type paper machine, paper making is carried out by a conventional method.

Processing of non-combustible sheet with moisture-proof / water-proof material and reinforcing material: The non-combustible sheet obtained by the above method can be combined and integrated with phenol resin foam to be used as a heat insulating material. When used as a heat insulating base plate or a duct heat insulating material, it is necessary to further impart waterproofness, moisture resistance, strength, and heat ray reflection performance. In order to meet such a purpose, it is effective to use a laminated composite with a plastic film or a non-woven fabric, or an aluminum foil, a laminated composite inorganic sheet with an aluminum vapor deposition film, or a laminated composite with a glass non-woven fabric or glass paper. .. The selection criteria for the plastic film or the non-woven fabric depend on the thickness, but it is preferably water-insoluble and flame-resistant in view of moisture resistance and waterproofness. Suitable films for this purpose include, for example, a thin PE film, a PP film, a thin to medium PET film, a polyamide film, a vinyl chloride film, and a vinylidene chloride resin film. As a laminate with an aluminum foil or an aluminum vapor-deposited film, a foil obtained by spreading metallic aluminum, or a film obtained by vapor-depositing aluminum on a PET film or the like can be laminated by a method such as transferring to the inorganic sheet. Further, for the purpose of improving the adhesion with the phenol resin foam, it is preferable to form an oxide film by corona discharge treatment on the above-mentioned composite inorganic sheet, or to perform a treatment in which both methods are used in combination.

Phenolic resin foam: As the highly flame-retardant phenolic resin foam used in the present invention, any conventionally known phenolic resin foam can be used. Specifically, it also contains a powdery novolac type phenolic resin, a liquid aqueous or non-aqueous resol type phenolic resin, urethane, epoxy, melamine and urea modified phenolic resin. The phenol resin is prepared with a curing agent selected from amines such as hexamethylenetetramine, inorganic acids such as phosphoric acid and hydrochloric acid, organic acids such as paratoluenesulfonic acid and phenolsulfonic acid, and silicone-based nonionic surfactants. Phenolic resin foams obtained by blending a foaming agent such as a foaming agent or fluorocarbon and heat-foaming and curing can be mentioned.

Manufacturing method of composite heat insulating plate:
It will be joined and integrated with phenol resin foam, and finally it will take the form of a composite heat insulating material.The joining method is to put the non-combustible sheet on one or both sides at the stage of foam hardening the phenol resin and inject or apply foam hardening Let them be integrated. Non-combustible sheet is bonded and integrated on one side of phenol resin foam, and on the other side, gypsum board, rock wool hard board, calcium silicate board, asbestos cement board,
When a pulp cement plate, a wood wool cement plate, a veneer plate, a metal plate, a vinyl chloride sheet, a non-woven fabric, or paper is used, the same method as the above-mentioned compounding can be used. It is also possible to adopt a method of applying a commercially available adhesive such as an epoxy resin, a vinyl acetate resin, a rubber resin, etc. to the resulting phenol resin foam to integrate and bond it by post-processing. FIG. 1 to FIG. 4 are schematic views of the constitutional aspect of the composite heat insulating material of the present invention.
It is as follows. 1 is a composite heat insulating material composed of a non-combustible sheet 1 and a phenol resin foam 3, FIG. 2 is a composite heat insulating material composed of a non-combustible sheet 1-phenol resin foam 3-non-combustible sheet 1, and FIGS. , A non-combustible sheet 1-phenol resin foam 3-side material 2 is a composite heat insulating material. In particular, FIG. 4 shows one embodiment of the composite heat insulating material when the face material is a metal panel.

[0013]

EXAMPLES The present invention will now be described in more detail with reference to examples. (1) Structure of composite heat insulating material 84 parts by weight of phenol, 558 parts by weight of 37% formalin, and 11.1 parts by weight of calcium hydroxide were placed in a flask and allowed to undergo an isothermal reaction at 90 ° C. for 60 minutes, followed by brominated cresol monoglycidyl. After adding 85 parts by weight of ether and reacting for another 20 minutes, the pH of the reaction solution was 7.0 to 7.3.
Oxalic acid was added thereto to neutralize the reaction solution, and the reaction solution was neutralized and dehydrated under reduced pressure at 80 ° C. to obtain 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 1. A 9 wt% resol type phenol resin solution was obtained. 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 Co.), and 15 parts by weight of paratoluenesulfonic acid as a curing agent were added. Agent (flame retardant) 10 parts by weight of antimony trioxide was added, and a pH adjuster was added so that the pH of the mixture became neutral. Alternatively, it was supplied between a non-combustible sheet and a non-combustible sheet and heated at 70 ° C. for 20 minutes to foam and cure.

Example 1 (A) Phenolic resin foam: Density 42 kg / m ³ , thickness 16 mm. (B) Substrate: gypsum board, general commercial product, thickness 9 mm. (C) Face material: non-combustible sheet, 70% by weight of phosphoric acid bulb, 27% by weight of glass fiber (E glass, cut length 3 mm), 1% by weight of sulfuric acid band, binder vinylidene chloride resin emulsion (Kureha Chemical Co., Ltd. 2 The weight% was dispersed in water at a concentration of about 1% by weight, and paper was made by a conventional method to obtain a nonflammable sheet.

Example 2 (A) Phenolic resin foam: density 58 kg / m ³ , thickness 15 mm. (B) Substrate: calcium silicate plate, general commercial product, thickness 10
mm. (C) Face material: PE film (thickness: about 10 mm) laminated on the non-combustible sheet of [1], thickness: 0.28 mm.

Example 3 (A) Phenolic resin foam: density 45 kg / m ³ , thickness 13 mm. (B) Substrate: Rock wool hard plate, density 0.4, thickness 1
2mm, semi-incombustible (flame retardant second grade) type, Nitto Boseki Co., Ltd.
Mineraboard made by (C) Surface material: Non-combustible sheet of [2], corona discharge and simp processed at intervals of 2 inches, thickness 0.28 mm.

Example 4 (A) Phenol resin foam: density 62 kg / m ³ , thickness 25 mm. (B) Face material: Two sheets obtained by laminating an aluminum vapor deposition film (thickness of about 3 μ) on the non-combustible sheet of [1].

Example 5 (A) Phenolic resin foam: density 55 kg / m ³ , thickness 20 mm. (B) Substrate: Colored zinc hard plate, general commercial product, thickness 0.45
mm, polymer coated type. (C) Face material: Aluminum vapor-deposited film (thickness: about 3μ) and PE (thickness: about 10μ) are sequentially laminated on the non-combustible sheet of [1],
Corona discharge and Simp processing, thickness 0.29m
m.

Example 6 (A) Phenolic resin foam: density 50 kg / m ³ , thickness 25 mm. (B) Face material: Two noncombustible sheets of [1].

Example 7 A panel obtained by immersing the panel obtained in Example 6 in running hot water for 3 days and then drying it.

In the production of the above composite heat insulating material, the basic constitution is shown in FIGS.
Refer to FIG. 2 for Example 4 and Example 6, and FIG. 4 for Example 5.

Comparative Example 1 (A) Phenolic resin foam: density 50 kg / m ³ , thickness 25 mm. (B) Face material: 2 inorganic sheets, inorganic sheet--50% by weight aluminum hydroxide, 33% by weight L pulp, glass fiber (E glass, cut length 3 m
m) 10 wt%, fixing agent (Meisei Chemical Industry Co., Ltd. Phyrex RC107) 1 wt%, binder vinylidene chloride resin emulsion (Kureha Chemical Co., Ltd.) 2 wt% in water at a concentration of about 1 wt% And the paper was made by a conventional method to obtain an inorganic sheet.

Comparative Example 2 (A) Urethane resin foam: density 25 kg / m ³ , thickness 25 mm. (B) Face material: the non-combustible sheet used in Example 4.

(2) Performance of composite heat insulating material The adhesive properties between the face materials and the phenolic resin foams of the composite heat insulating materials of Examples 1 to 7 and Comparative Examples 1 and 2 produced as described above were visually evaluated after being peeled off by hand. .. Bending strength is JIS A95
14, the thermal conductivity was measured according to JIS A1423, and the fire resistance was measured according to the quasi-nonflammability test according to Ministry of Construction Notification No. 1231. The waterproof property was visually evaluated after being immersed in water for 24 hours. The characteristic values are shown in Table 1.

[0025]

[Table 1] 1) Pass ¹⁾ -Slight combustion gas generation. 2) Pass ²⁾ -Water does not penetrate into the foam layer. 3) Fail ³⁾ ─ When burned, there is no shape retention of the surface material and a large through hole reaching the back surface occurs. 4) Fail ⁴⁾ -A large amount of black smoke was generated when burning, and the original foam shape was not found. 5) Good ⁵⁾ ─ The resistance is large when peeled by hand, and the face material remains on the foam and peels between the face and paper. 6) Poor ⁶⁾ -There is no resistance when peeled by hand, and the face material peels off cleanly from the foam.

[0026]

Industrial Applicability As described above, the composite heat insulating material of the present invention is remarkably excellent in various properties such as fireproof property, heat insulating property, moisture proof property and mechanical property, and is useful as a material for various industrial fields in addition to building materials. is there. Furthermore, since the composite heat insulating material of the present invention is configured as described in detail and has excellent adhesion between the foamed phenolic resin layer and the surface material plate, heat insulation and interior construction can be easily performed, and the construction speed can be increased. Can be measured. Furthermore, since the foamed phenolic resin layer is flame-retardant and does not emit smoke or harmful gas, it can exhibit excellent practical effects.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a composite heat insulating material of the present invention in which a face material: a non-combustible sheet is joined and integrated on one side of a phenol resin foam.

FIG. 2 is a cross-sectional view of the composite heat insulating material of the present invention in which a face material: a non-combustible sheet is joined and integrated on both surfaces of a phenol resin foam.

FIG. 3 is a cross-sectional view of a composite heat insulating material of the present invention in which a face material: a non-combustible sheet is bonded and integrated on one surface of a phenol resin foam and a base material on the other surface.

FIG. 4 is a cross-sectional view of a composite heat insulating material of the present invention in which a face material: a non-combustible sheet is joined and integrated on one surface of a phenol resin foam, and the other surface other than the face of the face material is bonded so as to be wrapped with a base material.

[Explanation of symbols]

 1 Face material 2 Base material 3 Phenolic resin foam

Claims (3)

[Claims] 1. A composite heat insulating material comprising a phenol resin foam as a core material and a non-combustible sheet made of phosphorylated pulp bonded and integrated on one or both sides thereof. 2. A composite heat insulating material comprising a phenol resin foam as a core material, a non-combustible sheet made of phosphorylated pulp bonded to one or both sides thereof, and a moisture-proof waterproof material bonded to the surface of the non-combustible sheet. 3. A phenol resin foam as a core material, one side of which is joined with a non-combustible sheet of phosphorylated pulp, and the other side of which is a gypsum board, rock wool hard board, calcium silicate board, asbestos cement board, pulp cement board. ,
Metal plate, veneer board, wood wool cement board, wood chip cement board,
A composite heat insulating material obtained by joining and integrating base materials selected from the group consisting of vinyl chloride sheets, non-woven fabrics and paper.