JPH09278506A - Production of composite building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite building material excellent in flexural strength, etc., by bonding and hardening a fly ash-containing aggregate using a binder prepared by blending a phenol resin with a polyoxyethylene type nonionic surfactant. SOLUTION: A phenol resin-based binder is produced by bending 100 pts.wt. of a phenol resin (e.g. novolak phenol resin) solid at a normal temperature with 0.01-0.5 pt.wt. of a polyoxyethylene type nonionic surfactant (e.g. a polyoxyethylene alkyl phenyl ether). Then an aggregate comprising fly ash as an essential component and, if required, pumice, silica sand, aluminum hydroxide, calcium carbonate, alumina, glass fiber, etc., is bonded and hardened by using the phenol resin to produce the objective composite building material. The prepared composite building material is excellent in processability and is widely usable as an interior building material such as floor covering material, wall material, ceiling material and an exterior building material such as roof material, external wall material, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite building material in which an inorganic aggregate such as fly ash is bound with a phenol resin based resin binder.

[0002]

2. Description of the Related Art It is known that a composite building material is manufactured by mixing a phenol resin binder with an inorganic aggregate such as fly ash, fibers, etc., followed by pressure molding using a heating mold. No. 57, Japanese Patent Publication No. 57-303
It is known from Japanese Patent Publication No. 83 and the like. In these building materials, attempts have been made to improve the mechanical strength from the viewpoints of high performance of molded products, reduction of defective rate, and cost reduction. For this purpose, there are a method of lowering the molecular weight of the phenol resin to improve the flow, a method of adding an additive such as a silane coupling agent and an amide wax.

However, the method of lowering the molecular weight of the phenol resin to improve the flow has a limitation in reducing the molecular weight due to practical problems such as solidification when the solid phenol resin is used in a powder form. On the other hand, a silane coupling agent,
Although the method of adding an additive such as amide wax has a certain degree of strength improving effect, the effect is not directly proportional to the addition amount, and the effect is saturated or the strength is reduced from some point. There is also a method of using both together,
It cannot be said to be sufficient to dramatically improve the strength.

In addition to these methods, a method for improving the fluidity of the phenol resin at the time of melting by mainly mixing a liquid plasticizer has been proposed. There is a limit to the amount of compounding due to practical problems such as binding. Further, when it is used as a binder for a building material mainly composed of an inorganic aggregate such as fly ash, the mechanical strength is not significantly improved.

[0005]

Therefore, an object of the present invention is to make fly ash one of the main components of aggregate,
It is an object of the present invention to provide a method for producing a composite building material, which is obtained by binding this with a solid phenol resin-based binder, which has excellent mechanical strength and contributes to a reduction in defective rate and cost reduction.

[0006]

That is, according to the present invention, when a composite building material is manufactured by binding and curing an aggregate containing fly ash with a phenol resin binder, a polyphenol resin is added to 100 parts by weight of a solid phenol resin. A method for producing a composite building material, which comprises using a phenol resin-based binder prepared by mixing 0.01 to 0.5 part by weight of an oxyethylene type nonionic surfactant.

Hereinafter, the present invention will be described in detail. The composite building material according to the present invention is an inorganic-organic composite building material in which an aggregate containing fly ash as an essential aggregate component is bound and cured with a phenol resin binder. The fly ash used for this composite building material is typically coal ash collected in a pulverized coal burning thermal power plant or the like, but any fly ash can be used. In addition to fly ash, fibrous, granular, powdery, lumpy aggregates and reinforcing fibers can be used. Examples of such aggregates include inorganic aggregates such as pumice (volcanic debris), silica sand, aluminum hydroxide, calcium carbonate, alumina, talc, and mica. Of these, one kind may be used, or 2 You may use together 1 or more types. As the reinforcing fibers, for example, glass fibers, rock wool, inorganic fibers such as carbon fibers, and organic fibers such as polyester fibers can be used. It is preferable that the aggregate is mainly inorganic aggregate, but organic aggregate such as wood chips may be included. However, fly ash must be included as part of the aggregate, and preferably 20% of the aggregate.
It may be contained in an amount of not less than wt%, more preferably not less than 40 wt%. By doing so, a lightweight and high-strength composite building material can be obtained.

The phenol resin used in the present invention is not limited as long as it is solid at room temperature, and it is obtained by reacting phenols such as phenol, cresol and xylenol with formaldehyde in the presence of a catalyst. As long as it is a novolac type phenolic resin, a resol type phenolic resin, a modified phenolic resin thereof, or a resin mixture of these. These phenolic resins are used as solids in the presence or absence of hardeners. From the viewpoint of performance and workability, novolac type phenol resin is particularly preferable.

Further, the polyoxyethylene type nonionic surfactant used in the present invention is a nonionic surfactant obtained by addition-polymerizing ethylene oxide to alkylphenols, higher aliphatic alcohols, fatty acids and the like. Examples of such a polyoxyethylene type nonionic surfactant include, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether,
Polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene vegetable oil ether, polyoxyethylene allyl phenyl ether, polyoxyethylene perfluoroalkyl ether, and the like. Of these, one kind may be used, or two or more kinds may be used in combination. Other surfactants, for example, nonionic surfactants other than polyoxyethylene type, cationic surfactants or anionic surfactants do not sufficiently produce the effect of the present invention.

The mixing ratio of the polyoxyethylene type nonionic surfactant to the phenol resin is determined from the viewpoint of the strength of the molded product, but is preferably 0.01 to 0.5 parts by weight, preferably 100 parts by weight of the phenol resin. Is 0.03-
0.3 parts by weight. When two or more polyoxyethylene type nonionic surfactants are used in combination, it is the total amount. If the blending ratio is less than 0.01 parts by weight, the effect of improving the strength of the composite building material is not remarkable, and if it exceeds 0.5 parts by weight, only the effect as a bulking agent can be expected. When the binder is used in solid or powder form, problems may occur in practical use such as caking.

The above-mentioned phenol resin and the polyoxyethylene type nonionic surfactant may be mixed by any method. When the surfactant is solid, it is powdered and mixed, or it is ground together with the phenol resin. In addition to the method of mixing, when the surfactant is solid or liquid, a method of melt-mixing the two, a method of adding in the reaction or dehydration step of the phenol resin, etc. can be used, but are not limited thereto. Not something to do. In order to bring out the effect of improving the strength with a small blending ratio, it is preferable to mix as uniformly as possible, and from this point, the melt mixing method is more effective. Moreover, when manufacturing a composite building material without mixing in advance, you may add and mix both.

If necessary, the binder obtained by mixing the phenol resin and the polyoxyethylene type nonionic surfactant may be mixed with various additives such as a curing accelerator, a silane coupling agent and a lubricant. You can In the case of novolac resin, hexamethylenetetramine can be added. Since this binder is used as a binder for a composite building material containing an inorganic aggregate such as fly ash as a main component, it is mixed in a solid state, preferably in a powder state and used.

Next, a method for manufacturing the composite building material will be described. The following method can be used as a method for manufacturing a composite building material by binding and curing an aggregate containing fly ash with a phenol resin-based binder. First, a method of dry-mixing the inorganic aggregate containing fly ash and the binder, filling the mixture in a mold, and then heat-pressing the mixture, uniformly spraying the mixture on a caul plate, and forming a laminate. There is a method of heat and pressure molding, etc., and if necessary, reinforcing fibers such as glass fibers are dispersed and laminated to produce a composite building material. In the case of forming a laminate, a method of laminating a molding material obtained by variously combining an aggregate including fly ash, fibers, and a binder in a thin layer can be used.

The blending amount of the binder with respect to the aggregate containing fly ash is 5 to 3 with respect to 100 parts by weight of the aggregate.
It is 0 part by weight, preferably 10 to 20 parts by weight. If the amount of this binder is less than 5 parts by weight, the strength of the composite building material will not be sufficient, and if it exceeds 30 parts by weight, the flame retardancy will decrease, and the economical efficiency will be improved by using a large amount of expensive resin compared to the aggregate. Be damaged.

As a method of molding the composite building material as described above, a method of heat and pressure molding using a multi-stage hot press or the like can be used. The molding conditions are a temperature of 100 to 300 ° C., a pressure of 1 to 100 kg / cm ² , and a time of 1 mm although the time depends on the thickness of the molded product.
Per 0.5 to 5 minutes is preferable.

The composite building material produced in this manner has high mechanical strength and good workability. For example, floor material,
It is widely used as interior building materials such as wall materials and ceiling materials, and exterior building materials such as roof materials and outer wall materials. The term “improved mechanical strength” as used in the present invention means that the strength when the polyoxyethylene type nonionic surfactant is not added to the phenol resin is taken as a standard and the mechanical strength is improved at a significant level.

[0017]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The following method was used to evaluate the strength of the binder. A mixture obtained by uniformly mixing 100 parts by weight of fly ash and 15 parts by weight of a powdery binder was filled in a mold at room temperature and heated and pressed (16
0 ° C × 20 minutes, 20 kg / cm ² ) and 150 × 20 ×
Six 15 mm plate-shaped compacts were prepared for each condition, the density was measured, and then the bending strength was measured with a span of 100 mm.

Example 1 Polyoxyethylene nonyl phenyl ether (manufactured by Sanyo Kasei Co., Ltd.) was added to 100 parts by weight of a novolac type phenol resin (Sphenol NK-7000 manufactured by Nippon Steel Chemical Co., Ltd.) having a softening point of 100 ° C. Nonipol 400) 0.05
After 1 part by weight was melt mixed at 150 ° C., it was solidified. After adding 15 parts by weight of hexamethylenetetramine as a curing agent to the solidified mixture, the binder obtained by pulverizing was mixed with fly ash according to the method described above, molded, and evaluated.

Examples 2 to 3 Same as Example 1 except that the compounding amount of polyoxyethylene nonylphenyl ether was 0.1 parts by weight (Example 2) and 0.3 parts by weight (Example 3). Then, it was molded and evaluated.

Examples 4 to 6 Instead of polyoxyethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block polymer (New Pol PE manufactured by Sanyo Kasei Co., Ltd.)
-108) in an amount of 0.05 parts by weight (Example 4),
0.1 parts by weight (Example 5), 0.3 parts by weight (Example 6)
Molding and evaluation were performed in the same manner as in Example 1 except that

Examples 7 to 8 Instead of polyoxyethylene nonylphenyl ether, 0.01 part by weight of polyoxyethylene perfluoroalkyl ether (Unidyne DS-401 manufactured by Daikin Industries, Ltd.) was used (Example 7). ), 0.1 parts by weight (Example 8), and molding in the same manner as in Example 1,
evaluated.

Comparative Example 1 Molding and evaluation were carried out in the same manner as in Example 1 except that polyoxyethylene nonylphenyl ether was not added.

Comparative Example 2 100 parts by weight of a novolac type phenolic resin (S-phenol NK-7000 manufactured by Nippon Steel Chemical Co., Ltd.) having a softening point of 100 ° C. was added to a silane coupling agent (A-1100 manufactured by Nippon Unicar Co., Ltd.). ) 0.3 parts by weight and 3 parts by weight of ethylene bis-stearamide (EBS powder manufactured by Kao Corporation) were melt mixed at 150 ° C. and then solidified. Hexamethylenetetramine as a curing agent was added to the solidified mixture 15
After adding parts by weight, the binder obtained by crushing, according to the above method, mixed with fly ash, molded,
evaluated.

Comparative Example 3 Molded in the same manner as in Example 1 except that the compounding amount of polyoxyethylene nonylphenyl ether was 3 parts by weight,
evaluated.

Comparative Example 4 The same as Example 1 except that the anionic surfactant (Sansebara 100 manufactured by Sanyo Kasei Co., Ltd.) was used in an amount of 0.1 part by weight instead of polyoxyethylene nonylphenyl ether. It shape | molded and evaluated similarly.

Comparative Example 5 Example 1 was repeated except that the anionic surfactant (Chemist 3033 manufactured by Sanyo Chemical Industry Co., Ltd.) was used in an amount of 0.1 part by weight instead of polyoxyethylene nonylphenyl ether. It shape | molded and evaluated similarly.

Comparative Example 6 Example 1 was repeated except that the cationic surfactant (Cation S manufactured by Sanyo Kasei Co., Ltd.) was used in an amount of 0.1 parts by weight instead of polyoxyethylene nonylphenyl ether.
It shape | molded and evaluated similarly to.

Table 1 shows the evaluation results of the bending strength of the molded articles of Examples 1-8 and Comparative Examples 1-6. In addition, in Table 1, the value in () of the bending strength column indicates the standard deviation, and the strength ratio indicates the strength when Comparative Example 1 is set to 100.

[0029]

[Table 1]

From Table 1, it is recognized that the use of the phenol resin binder of the present invention significantly improves the bending strength of the molded product at a significant level as compared with the conventional phenol resin binder.

Next, a method for producing a composite building material composed of an inorganic aggregate containing fly ash as a main component, fibers and a phenol resin binder will be described with reference to Examples and Comparative Examples. In addition, the manufacturing method of the composite building material and the strength evaluation were based on the following methods. 12 kg of fly ash having an average particle size of 50 microns and 4 kg of powdered phenol resin are dry-mixed, and 1/4 of the mixture, 4 kg, is 1 m × of a caul plate.
It is sprinkled in a uniform thin layer over a range of 1 m, 0.5 kg of chopped strand-shaped glass fibers having a length of 2.5 cm are sprinkled evenly on it in a random orientation, and 4 kg of the mixture is further spread on it. To form a lower layer. Next, 4 kg of fly ash having an average particle size of 50 microns, 4 kg of pumice having an average particle size of 2 mm and 1 kg of powdered phenol resin are dry-mixed and uniformly dispersed on the lower layer to form an intermediate layer. Further, an upper layer was formed on the middle layer in the same manner as the lower layer to obtain a molding material having a three-layer structure. This molding material was set in a hot press and molded to a plate thickness of 2.5 cm under molding conditions of a temperature of 160 ° C., a pressure of 20 kg / cm ² , and a time of 25 minutes to produce a composite building material. 300 × 25 × 25 from the obtained composite building material
Six 6 mm test pieces were cut out, the density was measured, and then the bending strength was measured with a span of 250 mm.

Example 9 Polyoxyethylene nonyl phenyl ether (manufactured by Sanyo Kasei Co., Ltd.) was added to 100 parts by weight of a novolak type phenol resin (S-phenol NK-7000 manufactured by Nippon Steel Chemical Co., Ltd.) having a softening point of 100 ° C. Nonipol 400) 0.1 part by weight was melt-mixed at 150 ° C. and then solidified. Fifteen parts by weight of hexamethylenetetramine as a curing agent was added to the solidified mixture, and then the phenol resin binder obtained by crushing was used to manufacture a composite building material according to the above method, and evaluated.

Examples 10 to 11 Instead of polyoxyethylene nonylphenyl ether, polyoxyethylene-polyoxypropylene block polymer (New Pol PE manufactured by Sanyo Kasei Co., Ltd.)
-108) (Example 10), polyoxyethylene perfluoroalkyl ether (Unidyne DS-401 manufactured by Daikin Industries, Ltd.) (Example 11) was used, and a composite building material was produced in the same manner as in Example 9. And evaluated.

Comparative Example 7 A composite building material was produced and evaluated in the same manner as in Example 9 except that polyoxyethylene nonylphenyl ether was not added.

Comparative Example 8 100 parts by weight of a novolac type phenolic resin (S-phenol NK-7000 manufactured by Nippon Steel Chemical Co., Ltd.) having a softening point of 100 ° C. was added to a silane coupling agent (A-1100 manufactured by Nippon Unicar Co., Ltd.). ) 0.3 parts by weight and 3 parts by weight of ethylene bis-stearamide (EBS powder manufactured by Kao Corporation) were melt mixed at 150 ° C. and then solidified. Hexamethylenetetramine as a curing agent was added to the solidified mixture 15
After adding parts by weight, a composite building material was manufactured according to the above-mentioned method using a phenol resin binder obtained by crushing, and evaluated.

Comparative Example 9 A composite building material was produced and evaluated in the same manner as in Example 9 except that the compounding amount of polyoxyethylene nonylphenyl ether was 3 parts by weight.

Comparative Examples 10 to 11 Instead of polyoxyethylene nonylphenyl ether, an anionic surfactant (Sansebara 100 manufactured by Sanyo Kasei Co., Ltd.), a cationic surfactant (Cation S manufactured by Sanyo Chemical Co., Ltd.) ) Was used and a composite building material was manufactured and evaluated in the same manner as in Example 9.

Table 2 shows the evaluation results of the molded products of Examples 9 to 11 and Comparative Examples 7 to 12. In addition, in Table 2, the value in () of the bending strength column indicates the standard deviation, and the strength ratio is 1 in Comparative Example 9.
It is shown as 00.

[0039]

[Table 2]

[0040]

As described above, according to the present invention described above, it is possible to manufacture a composite building material in which the bending strength is significantly improved at a significant level as compared with the conventional method for manufacturing a composite building material.

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Claims (1)

[Claims] 1. When a composite building material is manufactured by binding and curing an aggregate containing fly ash with a phenol resin-based binder, 100 parts by weight of a solid phenol resin is added to a polyoxyethylene type nonionic surfactant of 0.1 part by weight. 01
A method for producing a composite building material, which comprises using a phenol resin-based binder obtained by mixing 0.5 to 0.5 parts by weight.