JP3097003B2 - Non-combustible phenolic resin foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-combustible building board such as a wall board which is excellent in lightweight, heat insulating property, surface design and flame retardancy.
In particular, it relates to a nonflammable phenolic resin foam used as a wall plate.

[0002]

2. Description of the Related Art Conventionally, calcium silicate boards, asbestos cement boards and the like have been used as non-combustible building boards, especially wall boards, but all of them lack heat insulation properties, are heavy, and have problems in workability. A phenolic resin foam which is lightweight and has excellent heat insulating properties and workability is being adopted. Further, in order to impart a design property to the phenolic resin foam and reinforce the surface, a surface decorative sheet such as a wooden veneer, a decorative veneer, or a plastic sheet is adhered to the surface.

[0003]

However, the conventional phenolic resin foam has a porous surface and is highly water-absorbing, so that the applied adhesive rapidly penetrates into the foam and can be used for wooden veneer, decorative veneer or surface decorative sheet. There was a problem that adhesion was difficult. For this reason, surface paper such as kraft paper, aluminum hydroxide paper, calcium carbonate paper, etc., was integrally joined to the surface of the resin foam during foaming and curing of the phenolic resin. There is a problem that the flame retardancy of the resin foam decreases. Also, surface paper such as kraft paper, aluminum hydroxide paper and calcium carbonate paper has poor air permeability, which prevents the diffusion of a large amount of water generated during curing of the phenol resin, and tends to cause gas swelling and void defects. Was.
In addition, since the phenolic resin does not penetrate into kraft paper, aluminum hydroxide paper, and calcium carbonate paper, the adhesive strength between the phenolic resin foam and the facing paper and the peeling strength of the facing paper are weak, and the surface decorative sheet is not used. When they are bonded, there is a problem that the surface decorative sheet is easily peeled off even by a slight external force. In addition, there is a problem that a large difference is caused in the air permeability between the front and back surfaces due to the adhesion of the surface decorative sheet, and warpage occurs over time. The present invention has a high adhesive strength between the phenolic resin foam and the face paper, and a high peel strength between the face paper and paper, and has excellent flame retardancy, and can be easily bonded when the surface decorative sheet is bonded to the surface, and is warped. It is an object of the present invention to provide a non-combustible phenol resin foam which does not cause any odor.

[0004]

The object of the present invention is to provide a resol type phenolic resin of the present invention with an acid curing agent, a foaming agent and a foam stabilizer.
The mixture obtained by adding and mixing is subjected to an air permeability of 10 seconds / inch φ3
Spread at least one layer of glass paper of 100 cc or less
After pouring, air permeability is 10 seconds / inch φ300 on the mixture.
Place one or more layers of glass paper of cc or less,
The problem is solved by a foam, a non-combustible phenolic resin foam having a cured and formed density of 0.1 to 0.5 g / cm ³ . This will be described below.

The phenolic resin used for producing the resole type phenolic resin foam of the present invention includes phenols such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol and resorcinol, and modified products thereof and formaldehyde, paraformaldehyde, It is a resol type produced by reacting aldehydes such as furfural and acetaldehyde with an alkaline catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide, hexamethylenetetramine, trimethylamine and triethylamine.

The acid curing agent used for producing the resole type phenolic resin foam of the present invention includes inorganic acids such as sulfuric acid and phosphoric acid, benzenesulfonic acid, naphtholsulfonic acid, and the like.
Organic acids such as phenolsulfonic acid are exemplified.

The blowing agents used in the present invention include low-boiling aliphatic hydrocarbons such as pentane, hexane and heptane; ethers such as isopropyl ether; chlorinated aliphatic hydrocarbons such as methylene chloride; trichloromonofluoromethane; Fluorine compounds such as trichlorotrifluoroethane,
Alternatively, a mixture of these compounds is included.

As the foam stabilizer used for producing the resol type phenolic resin foam of the present invention, a foam stabilizer such as a silicone-based nonionic surfactant is used.

Further, aluminum hydroxide may be added as a filler in order to improve the flame retardancy of the phenolic resin foam, and other additives may be added as required.

The air permeability used as a face material in the present invention is 1
Glass paper of 0 seconds / inch φ300 cc or less can be made by a conventional paper machine using a paper machine of a long net type, a circular net type, a rotoformer type, an inclined type or the like, but may be selected from commercially available ones. The glass paper of the present invention includes glass pulp mixed paper, glass non-woven fabric, and glass paper such as glass pulp mixed paper and glass non-woven fabric which have been subjected to a resin impregnation treatment and coloring as required. When the air permeability of the glass paper of the present invention is 10 seconds / inch φ300 cc or more, the non-flammable phenol resin does not sufficiently penetrate into the glass paper, so that the surface decorative paper is easily peeled off from the non-flammable phenol resin foam, and the flame retardancy is reduced. I do. In addition, the glass paper of the present invention can be used more than one layer, and the air permeability of the front and back is adjusted by changing the number of superposed glass papers on the front and back of the non-combustible phenol resin foam to warp the non-combustible phenol resin foam. Can be prevented from being deformed.

The non-combustible phenolic resin foam of the present invention is obtained by mixing a mixture of the resole type phenolic resin with an acid curing agent, a foaming agent, a foam stabilizer and the like, and having an air permeability of 10 seconds / hour.
One layer of glass paper of inchφ300cc or less
After pouring on the spread, air permeability over the mixture is 10 seconds / in
Place one or more layers of glass paper of chφ300cc or less
And obtained by heating and foaming. Density is 0.1-0.5g /
Adjustment to cm ³ is preferable from the viewpoint of physical properties of the plate, particularly, bending strength and compressive strength.

[0012]

Since one or more layers of glass paper having an air permeability of 10 seconds / inchφ300 cc or less are bonded to both surfaces of the non-combustible phenol resin foam of the present invention and the air permeability is adjusted, phenol is used. Dispersion of a large amount of water generated during curing of the resin is dissipated to the outside without being hindered, and the applied adhesive does not rapidly penetrate into the foam and acts effectively, facilitating the adhesion of the surface decorative sheet etc. Ru strongly Re I line <br/>. Furthermore, the air permeability of the front and back surfaces is also adjusted by changing the type of glass paper and the number of sheets to be superposed.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments. Phenol resin: 84 parts by weight of phenol, 558 parts by weight of 37% formalin, and 11.1 parts by weight of calcium hydroxide are charged into a flask, and subjected to isothermal reaction at 90 ° C. for 60 minutes, and then 85 parts by weight of brominated cresol monoglycidyl ether After reacting for further 20 minutes,
The reaction solution was neutralized by adding oxalic acid so that the pH of the solution became 7.0 to 7.3, dehydrated at 80 ° C. under reduced pressure, and resol of 3.0% by weight of free phenol and 1.9% by weight of free formalin. A phenolic resin was obtained. Using this phenolic resin, phenolic resin foams of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained, and the physical properties were measured. The results are shown in Tables 1 and 2.

[0014]

[Table 1]

[0015]

[Table 2]

[Examples 1 to 4] 100 parts by weight of phenol resin, foam stabilizer (L-5340 manufactured by Union Carbide)
0.2 parts by weight, 59 parts by weight of aluminum hydroxide, 3 parts by weight of a foaming agent (methylene chloride), and 11 parts by weight of a curing agent (p-toluenesulfonic acid) were uniformly mixed, and previously shown in the column on the back of Table 1. Wooden frame (220mm
× 220 mm × 10 mm), and put thereon the glass paper shown in the column of the surface material in Table 1 at 80 ° C.
The mixture was heated for 0 minutes, foamed, and cured to obtain a non-combustible phenol resin foam of the present invention.

Comparative Examples 1 to 3 A phenolic resin foam was obtained in the same manner as in Example except that the papers shown in the front and back surfaces of the face material in Table 2 were used instead of the glass paper.

[Measurement] Penetration of phenolic resin into face material: Penetration of the phenolic resin into the outermost face material was visually determined. Combustion test: According to JIS A 1321. Adhesion of surface decorative sheet: Natural wood veneer (oak) was adhered at a coating amount of vinyl acetate resin emulsion of 110 g / m ^{2, and} measured and judged by a tape peeling test. Warpage resistance: A worm yarn was stuck on a board and left at 20 ° C. and 60 RH for 2 weeks, and the gap between the worm yarn and the foam was visually determined.

[0019]

The non-combustible phenolic resin foam of the present invention uses a glass paper having an air permeability of 10 seconds / inch φ300 cc or less as a face material, so that a large amount of water generated during curing of the phenolic resin is prevented from diffusing. No gas swelling or void defects occur. Also, since the phenol resin penetrates into the face paper, the adhesive strength between the phenolic resin foam and the face paper, the peel strength between the face paper and the face paper and the decorative sheet can be easily achieved, and The adhesive strength is so strong that it is not easily peeled off by external force. Furthermore, since the air permeability of the front and back can be adjusted by changing the number of superposed sheets, deformation such as warpage of the non-combustible phenol resin foam can be prevented. Therefore, when the non-combustible phenolic resin foam of the present invention is used as a non-combustible building board for a wall or the like, the above-described excellent performance is obtained.

Claims (1)

(57) [Claims] 1. An acid curing of a resol type phenol resin
The mixture obtained by adding the agent, the foaming agent, and the foam stabilizer is injected onto one or more layers of glass paper having an air permeability of 10 seconds / inch φ300 cc or less , and then the air permeability is 10
1 layer of glass paper of less than 300cc / inchφ
Placed above, heated, foamed, cured formed density 0.1 ~
0.5 g / cm ³ non-combustible phenolic resin foam.