JP2592338Y2 - Composite insulation - Google Patents

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 core of a urethane-modified phenol resin foam which is excellent in fireproof heat insulating properties and is used in construction and various other industrial fields.

[0002]

2. Description of the Related Art Conventionally, a phenol resin foam having excellent flame retardancy and fire resistance has been used as a heat insulating material in construction and other industrial fields. Although the phenolic resin foam has such excellent performance, it has weaker adhesiveness to the face material and weakness in physical performance such as strength and flyability as compared with other plastic foams. In order to compensate for such weaknesses in performance and further enhance fire resistance, increase the foam density, composite with various inorganic sheets or face materials such as flame-retardant organic sheets, further, gypsum board, asbestos It is practically used in a composite form with a cement plate, a calcium silicate plate, a metal plate, and the like. In particular, a composite heat insulating material of a phenolic resin foam-asbestos-containing inorganic sheet is most widely used.

[0003]

However, there are the following problems in the face material that is composited with the conventional phenolic resin foam. Therefore, a heat insulating material that is still practically sufficiently satisfactory has been provided to the market. Not. First, as the conventional inorganic sheet, an inorganic sheet containing asbestos fiber, an inorganic sheet containing an inorganic powder such as aluminum hydroxide or calcium carbonate is used as a face material, and a flame retardant impregnated with a flame retardant is used as an organic sheet. Organic sheets such as treated paper are used as face materials. Inorganic sheet containing asbestos fiber has good performance as a surface material without sacrificing the fire resistance of phenolic resin foam, but asbestos fiber is specified as a specific chemical substance, preventing pollution and working environment and hygiene. Subject to usage restrictions,
Currently, use is banned in some countries. Although the inorganic sheet containing an inorganic powder such as aluminum hydroxide or calcium carbonate is nonflammable, it does not have shape retention of the surface material during combustion and has no positive effect on fire resistance. In particular, the inorganic powder has poor adhesion to the phenolic resin foam and therefore has a weak reinforcing effect as a face material. Although the flame retardant treated organic sheet impregnated with the flame retardant improves the phenolic resin foam in terms of physical performance, since the flame retardant is mixed with the pulp, the pulp deteriorates, deteriorates, and discolors.
The fire resistance is negative because the flame retardancy is reduced or disappears when wet with water during use. Furthermore, the inorganic sheet and the organic sheet have insufficient moisture-proof and water-proof properties, and there is a problem that the heat-insulating performance is reduced due to moisture permeability of the heat-insulating material after construction. As described above, the inorganic sheet and the organic sheet conventionally used as the surface material for the phenolic resin foam have insufficient fire resistance, have environmental health problems (asbestos toxicity, skin irritation), There are problems in that the adhesiveness to the phenolic resin foam is insufficient, the handling property is poor, the economy (expensive), and the reinforcing property as a surface material is high.

[0004] In view of the above problems, the present invention provides a non-combustible sheet which is lightweight, has excellent heat insulating properties, excellent flame retardancy and fire resistance, and has excellent properties such as strength, flyability, environmental hygiene, moisture resistance and waterproofness. An object of the present invention is to provide a composite heat insulating material in which a urethane-modified phenolic resin foam is joined and integrated.

[0005]

The object of the present invention is to provide (1) a composite heat insulating material comprising a core made of a urethane-modified phenolic resin foam and a non-combustible sheet made of phosphorylated pulp joined and integrated on one or both sides thereof. (2) A composite heat insulating material comprising a urethane-modified phenolic resin foam as a core material, a non-combustible sheet made of phosphorylated pulp joined to one or both surfaces thereof, and a moisture-proof and waterproof material joined to the non-combustible sheet. (3) Urethane-modified phenol resin foam as the core material, a non-combustible sheet made of phosphorylated pulp bonded to one side, and a gypsum board, rock wool hard board, calcium silicate board, asbestos cement board, pulp cement board on the other side A composite heat insulating material obtained by joining and integrating a base material selected from the group consisting of a metal plate, a veneer plate, a wood wool cement plate, a wood chip cement plate, a vinyl chloride sheet, a nonwoven fabric and paper.
Solved by Hereinafter, the composite heat insulating material of the present invention will be described in detail.

Construction of the 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 components containing a fiber substance, a binder and / or other additives are dispersed in water as required. Can be Phosphorylated pulp, which is an essential component, is obtained by chemically bonding ammonium phosphate to cellulose.

Embedded image Having the chemical formula The amount of the phosphorylated pulp used in the non-combustible sheet of the present invention is 30 to 100% by weight. 30% by weight
If the amount is smaller, the shape retention of the face material during combustion is insufficient. Glass fibers, ceramic fibers, rock wool fibers and the like can be mentioned as the inorganic fibers to be blended if desired. The content of the inorganic fibers is 70% by weight or less. If the content exceeds 70% by weight, the foldability of the non-combustible sheet and the workability such as irritation of the skin are reduced.

With respect to the above-mentioned composition, paper strength such as tensile strength when wet, papermaking retention of a solid composition (retention),
An organic fiber, an organic binder, a fixing agent, a sizing agent, a colorant and the like are added in a total amount of 30% by weight or less for the purpose of improving papermaking properties (filtration), imparting water repellency to the sheet, 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.

[0008] Examples of the organic binder include acrylic resin, vinylidene chloride resin, synthetic rubber such as SBR and NBR, and thermosetting resin powder and emulsion such as ethylene vinyl acetate resin and phenol resin. Representative examples of the fixing agent include a sulfuric acid band and polyacrylamide.
As sizing agents, glue, alkyl ketene dimer,
Rosin size, wax emulsion, and the like. As the coloring agent, an organic / inorganic composite or inorganic general commercially available pigment can be used.

Production of non-combustible sheet: The production of the non-combustible sheet of the present invention is to uniformly prepare a predetermined proportion of phosphorylated pulp, fiber material, binder and other additives at a solid content of 0.5% by weight or more in a large amount of water. Fourdrinier type (Ford linear type),
Circular mesh type (Oliver type), funnel former type,
The paper is made by a conventional method using a paper machine such as an inclined type.

Processing of a non-combustible sheet with a moisture-proof / water-proof material and a reinforcing material: The non-combustible sheet obtained by the above-mentioned method can be used as a heat insulating material by bonding and integrating with a urethane-modified phenolic resin foam, for example, as a direct-cast concrete type When used as a heat insulating base plate or a duct heat insulating material, it is necessary to further impart waterproofness, moistureproofness, strength, and heat ray reflection performance. In order to meet this purpose, it is effective to use a laminate composite with a plastic film or a nonwoven fabric, or a laminate composite with an aluminum foil or an aluminum vapor-deposited film, or a laminate composite with a glass nonwoven fabric or a glass paper. .
Selection criteria for plastic film or non-woven fabric are:
Although it depends on the thickness, a material that is hardly soluble in water and flame resistant is preferable from the viewpoint of moisture resistance and waterproofness. Suitable films for this purpose include, for example, a thin PE film or a PP film, a thin to medium PET film, a polyamide film, a vinyl chloride film, and a vinylidene chloride resin film. Aluminum foil, foil with metal aluminum extended as a laminate with aluminum vapor deposition film, or PET
Aluminum film deposited on a film or the like can be laminated on the inorganic sheet. Further, for the purpose of improving the adhesion to the urethane-modified phenol resin foam, it is preferable to subject the above-mentioned composite inorganic sheet to corona discharge treatment, formation of an oxide film, or treatment using both methods in combination.

Urethane-modified phenolic resin foam:
The highly flame-retardant urethane-modified phenolic resin foam used in the present invention includes novolak-type phenolic resin, resol-type phenolic resin, benzylic ether-type phenolic resin, polyols such as polyether polyols and polyester polyols, and isocyanates such as MDI and TDI. And a foaming agent such as dichloromonofluoroethane, a foam stabilizer such as a silicone-based surfactant, a catalyst such as potassium octylate and a tertiary amine, and a flame retardant such as TCEP and antimony trioxide. Things.

Manufacturing method of composite heat insulating plate:
It is bonded and integrated with urethane-modified phenolic resin foam and finally takes the form of a composite heat insulating material.As a joining method, at the stage of foaming and curing urethane-modified phenolic resin, a non-combustible sheet is placed on one or both sides and injected. Alternatively, the resin is foamed and cured to be integrated. Non-combustible sheet is bonded and integrated on one side of urethane-modified phenolic resin foam, and on the other side, gypsum board, rock wool hard board, calcium silicate board, asbestos cement board, pulp cement board, wood wool cement board, veneer board, metal board , A vinyl chloride sheet, a nonwoven fabric, and paper can be used in the same manner as in the above-mentioned combination. Further, a method of applying a commercially available adhesive such as an epoxy resin, a vinyl acetate resin, a rubber-based resin, or the like to the resulting urethane-modified phenolic resin foam, and performing a post-processing joint for integration can be employed. FIG. 1 shows the configuration of the composite heat insulating material of the present invention.
5 to FIG. FIG. 1 shows a composite heat insulating material composed of a non-combustible sheet 1 and a urethane-modified phenolic resin foam 3, and FIG. 2 shows a composite heat insulating material composed of a non-combustible sheet 1-a urethane-modified phenolic resin foam 3 and a non-combustible sheet 1. FIGS. Is a composite heat insulating material composed of a noncombustible sheet 1, a urethane-modified phenolic resin foam 3, and a substrate 2. In particular, FIG. 4 shows one embodiment of the composite heat insulating material when the base material is a metal plate. FIG. 5 shows a composite heat insulating material in which a surface material obtained by laminating a moisture-proof / waterproof material and a reinforcing material on a non-combustible sheet is joined to one surface of a urethane-modified phenol resin foam.

[0013]

EXAMPLE The structure of the composite heat insulating material 100 parts by weight of phenol and 60.4 parts by weight of 37% formalin were charged into a flask, and 1 part by weight of oxalic acid was added and mixed.
The mixture was gradually heated, and an isothermal reaction was performed at 95 ° C. for 90 minutes. Then, after dehydration at 130 ° C. under reduced pressure, 1 part by weight of sodium hydroxide was added, and 112 parts by weight of propylene oxide was gradually added. The mixture was reacted for 2 hours and neutralized with acetic acid to obtain a novolak phenol resin containing 0.6% of free phenol. . Next, 160 parts by weight of the obtained phenol resin was mixed with polyether polyol (SBU-manufactured by Sumitomo Bayer Urethane Co., Ltd.).
0474) 40 parts by weight, a foam stabilizer (SH0193 manufactured by Toray Silicone Co., Ltd.) 4 parts by weight, potassium octylate 6 parts by weight, HCFC-141b 30 parts by weight, flame retardant TC
310 parts by weight of 7 parts by weight of EP and 310 parts by weight of crude MDI (44V-20 manufactured by Sumitomo Bayer Urethane Co., Ltd.) are blended and supplied to a non-combustible sheet between a non-combustible sheet and a non-combustible sheet or a non-combustible sheet having the following constitution, and the mixture is supplied at 75 ° C. For 15 minutes to foam and harden.

Example 1 (A) Urethane-modified phenolic resin foam: density 30
kg / m ³ , thickness 16 mm. (B) Base material: gypsum board, general commercial product, thickness 9 mm. (C) Face material: non-combustible sheet, phosphorylated pulp 70% by weight, glass fiber (E glass, cut length 3 mm) 27% by weight, sulfuric acid band 1% by weight, binder vinylidene chloride resin emulsion (manufactured by Kureha Chemical Co., Ltd.) 2% by weight about 1% by weight in water
And a paper was made by a conventional method to obtain a non-combustible sheet.

Example 2 (A) Urethane-modified phenolic resin foam: density 40
kg / m ³ , thickness 15 mm. (B) Base material: calcium silicate plate, general commercial product, thickness 10
mm. (C) Face material: The non-combustible sheet of [1] laminated with a PE film (about 10 μm thick), 0.28 m thick
m.

Example 3 (A) Urethane-modified phenolic resin foam: density 40
kg / m ³ , thickness 13 mm. (B) Base material: rock wool hard plate, specific gravity 0.4, thickness 1
2mm, quasi-noncombustible (second grade of flame-retardant) type, Minera board manufactured by Nitto Boseki Co., Ltd. (C) Surface material: Non-combustible sheet of [2] subjected to corona discharge and simp processing at 2-inch intervals, thickness 0.28mm .

Example 4 (A) Urethane-modified phenolic resin foam: density 40
kg / m ³ , thickness 25 mm. (B) Face material: Aluminum foil (approximately 7
.mu.) with a PE film (about 10 .mu.m thick) having a thickness of 0.29 mm.

Example 5 (A) Urethane-modified phenolic resin foam: density 30
kg / m ³ , thickness 20 mm. (B) Base material: colored zinc hard plate, general commercial product, thickness 0.45
mm, polymer coat treatment type. (C) Face material: A non-combustible sheet of [1] laminated with an aluminum vapor-deposited film (thickness of about 3 μ) with a PE sheet (thickness of about 10 μ), and subjected to corona discharge and simp processing, thickness of 0.2
8 mm.

Example 6 (A) Urethane-modified phenolic resin foam: density 33
kg / m ³ , thickness 25 mm. (B) Face material: Two non-combustible sheets of [1].

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

In the production of the above-mentioned composite heat insulating material, FIG. 3 shows [Basic constitution] in [Embodiment 1] to [Embodiment 3], [Embodiment 4], [Embodiment 6] and [Embodiment 6]. 7]
2 and FIG. 4 for [Embodiment 5].

Comparative Example Structure of Composite Insulating Material 84 parts by weight of phenol, 87 parts by weight of 37% formalin,
Put 11.1 parts by weight of calcium hydroxide into a flask,
The mixture was allowed to react isothermally at 90 ° C. for 60 minutes, and then 85 parts by weight of brominated cresol monoglycidyl ether was added.
After reacting for 0 minutes, oxalic acid was added so that the pH of the reaction solution became 7.0 to 7.3, and the reaction solution was neutralized.
Dehydrate at 89 ° C., solid content 89% by weight, viscosity at 30 ° C. 5
A resol-type phenol resin solution containing 7 poise, 3.0% by weight of free phenol and 1.9% by weight of free formalin was obtained.
20 parts by weight of trichlorofluoromethane as a foaming agent, 0.2 parts by weight of a foam stabilizer (L-5340 manufactured by Union Carbide), 15 parts by weight of paratoluenesulfonic acid as a curing agent, and 100 parts by weight of the resin liquid, (Flame retardant) After mixing 10 parts by weight of antimony trioxide and further adding a pH adjuster so that the pH of the blend becomes neutral, the mixture is added between a non-combustible sheet and a substrate having the following constitution or non-combustible. It was supplied between the sheet and the non-combustible sheet and heated at 70 ° C. for 20 minutes to foam and cure.

Comparative Example 1 (A) Phenolic resin foam: density 42 kg / m ³ ,
16mm thick. (B) Base material: gypsum hose, general commercial product, thickness 9 mm. (C) Face material: non-combustible sheet of Example 1

Comparative Example 2 (A) Phenolic resin foam: density 58 kg / m ³ ,
15mm thick. (B) Base material: calcium silicate plate, general commercialization, thickness 10 m
m. (C) Face material: Laminated PE film (about 10 μm thick) on the non-combustible sheet of Example 1, 0.28 m thick
m.

Comparative Example 3 (A) Phenolic resin foam: density 45 kg / m ³ ,
13mm thick. (B) Base material: rock wool hard plate, specific gravity 0.4, thickness 1
2mm, quasi-incombustible (second grade flame retardant) type, mineral board manufactured by Nitto Boseki Co., Ltd. (C) Face material: the non-combustible sheet of Comparative Example 2 subjected to corona discharge and symptom processing at intervals of 2 inches, thickness 0.28 m
m.

Comparative Example 4 (A) Phenolic resin foam: density 62 kg / m ³ ,
25mm thick. (C) Face material: Two sheets obtained by laminating an aluminum foil (about 7 μm in thickness) on the non-combustible sheet of Example 1 with a PE film,
The thickness is 0.29 mm.

Comparative Example 5 (A) Phenolic resin foam: density 55 kg / m ³ ,
20mm thick. (B) Base material: colored zinc hard plate, general commercial product, thickness 0.45
mm, polymer coat treatment type. (C) Face material: The non-combustible sheet of Example 1 was laminated with a vapor-deposited aluminum film (thickness: about 3 μm) using a PE sheet, subjected to corona discharge and simp processing, and had a thickness of 0.28 mm.

Comparative Example 6 (A) Phenolic resin foam: density of 50 kg / m ³ ,
25mm thick. (C) Face material: Two non-combustible sheets of Example 1.

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

Comparative Example 8 (A) Urethane-modified phenol resin foam: density 25
kg / m ³ , thickness 25 mm. (B) Face material: 2 inorganic sheets Inorganic sheet: 50% by weight of aluminum hydroxide, 33% by weight of L pulp, glass fiber (E glass, cut length 3m)
m) 10% by weight, 1% by weight of a fixing agent (Pyrex RC107 manufactured by Meisei Chemical Industry Co., Ltd.), 2% by weight of a binder vinylidene chloride resin emulsion (manufactured by Kureha Chemical Co., Ltd.) in an amount of about 1% by weight in water. The resulting mixture was dispersed at a predetermined concentration and paper-made by a conventional method to obtain an inorganic sheet.

Comparative Example 9 (A) Urethane resin foam: density 25 kg / m ³ , thickness 25 mm. (B) Face material: non-combustible sheet used in Comparative Example 4.

[Performance of Composite Thermal Insulation Material] Adhesion between the facing material of the composite thermal insulation materials produced in Examples 1 to 7 and Comparative Examples 1 to 9 and the urethane-modified phenolic resin foam was visually evaluated after peeling by hand. did. Flyability is based on ASTM C-421, foam density,
The bending strength is in accordance with JIS A-9514, and the thermal conductivity is in accordance with J
According to IS A-1412 and fire protection is JIS A-
1321. Water resistance was visually evaluated after immersion in water for 24 hours. The characteristic values are shown in Tables 1 and 2.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Effects of the Invention] As described above, the composite heat insulating material of the present invention is remarkably excellent in various performances such as light weight, fire resistance, heat insulation, moisture resistance, mechanical properties, and is used as a material in various industrial fields in addition to building materials. Useful. Furthermore, since the composite heat insulating material of the present invention is configured as described in detail and has excellent adhesion between the urethane-modified-phenolic resin foam layer and the surface material plate, heat insulation and interior work can be easily performed. Speed up can be measured. Furthermore, since the urethane-modified phenolic resin foam layer is flame-retardant and does not emit smoke or generate harmful gases, excellent practical effects can be exhibited.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a composite heat insulating material of the present invention in which a face material (non-combustible sheet) is integrally joined to one surface of a urethane-modified phenol resin foam.

FIG. 2 is a cross-sectional view of the composite heat insulating material of the present invention in which face materials (non-combustible sheets) are joined and integrated on both sides of a urethane-modified phenol resin foam.

FIG. 3 is a cross-sectional view of the composite heat insulating material of the present invention in which a face material (non-combustible sheet) is joined and integrated with one surface of a urethane-modified phenolic resin foam on one surface.

FIG. 4 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 one side of a urethane-modified phenolic resin foam, and the other faces other than the face material are joined so as to be wrapped with the base material. is there.

FIG. 5 is a cross-sectional view of the composite heat insulating material of the present invention in which a face material (a moisture-proof / water-proof material and a reinforcing material laminated on a non-combustible sheet) is integrally joined to one surface of a urethane-modified phenol resin foam.

[Explanation of symbols]

 1: face material 2: base material 3: urethane-modified phenolic resin foam 4: non-combustible sheet 5: moisture-proof / water-proof material, reinforcing material

Claims (3)

(57) [Scope of request for utility model registration] 1. A composite heat insulating material in which a urethane-modified phenolic resin foam is used as a core material, and a noncombustible sheet made of phosphorylated pulp is joined and integrated on one or both surfaces thereof. 2. A composite heat insulating material comprising a urethane-modified phenolic resin foam as a core material, a non-combustible sheet made of phosphorylated pulp joined to one or both surfaces thereof, and a moisture-proof waterproof material joined to the non-combustible sheet. 3. A urethane-modified phenolic resin foam as a core material, a non-combustible sheet made of phosphorylated pulp is joined to one surface of the core material, and a gypsum board, a rock wool hard plate, a calcium silicate plate, an asbestos cement plate, a pulp are attached to the other surface. Cement board, metal board, plywood board, wood wool cement board,
A composite heat insulating material obtained by joining and integrating a base material selected from the group consisting of a wood chip cement board, a vinyl chloride sheet, a nonwoven fabric and paper.