JPH09278507A - Production of composite building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a composite building material capable of not damaging utility of a solid phenol resin, improving mechanical strength, exhibiting excellent releasability and contributing to reduction in fraction defective, improvement in workability and reduction in cost. SOLUTION: In producing a composite building material by bonding and hardening an aggregate containing fly ash with a phenol resin-based binder, one obtained by blending 100 pts.wt. of a solid phenol resin with 2-8 pts.wt. of one or more plasticizer selected from p-toluenesulfonamide, dicyclohexyl phthalate and triphenyl phosphate, 0.1-5 pts.wt. of a wax having <1 poise melt viscosity at 150 deg.C and <=5% compatibility with a phenol resin and/or 1-20 pts.wt. of a thermoplastic resin having 1-1,000 poise melt viscosity at 150 deg.C and <=20% compatibility with the phenol resin is used as the phenol resin-based binder.

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 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 mechanical strength and releasability from the viewpoints of high performance of molded products, reduction of defective rate, improvement of workability, and cost reduction.

As a method of improving the mechanical strength, there are a method of lowering the molecular weight of a 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 reducing 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 phenol resin is used in a solid state, particularly in a powder state. Further, although the method of adding an additive such as a silane coupling agent or an amide wax has a certain degree of strength improving effect, it is not directly proportional to the addition amount, and the effect is saturated from a certain point. There is also a method of using both in combination, but the mechanical strength is not significantly improved and it cannot be said to be sufficient.

On the other hand, as a method for improving the releasability at the time of molding, a method of coating or spraying a mold releasing agent such as a silicone type or a fluorine type on a mold, a method of adding a fatty acid or its metal salt to a binder, etc. However, the former requires frequent application or spraying of a release agent in order to ensure releasability, which causes a problem of mold stains. In the latter case, not only the blending amount is limited due to practical problems, but also the releasing effect is not sufficiently obtained. There is also a method of using both in combination, but it is hard to say that this is sufficiently effective.

[0005]

Therefore, the object of the present invention is to improve the mechanical strength without impairing the practicality of the solid phenolic resin, and to exhibit excellent releasability during molding. An object of the present invention is to provide a manufacturing method of a composite building material which contributes to reduction of defective rate, improvement of workability 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 para resin is added to 100 parts by weight of a solid phenol resin. 2-8 parts by weight of one or more plasticizers selected from toluenesulfonamide, dicyclohexyl phthalate and triphenyl phosphate, and a melt viscosity at 150 ° C. of 1
0.1-5 parts by weight and / or 1 wax having a compatibility with a phenolic resin at 150 ° C. of less than 5% and less than poise.
Melt viscosity at 50 ° C is 150 at 1-1000 poise
A method for producing a composite building material, which comprises using a phenol resin-based binder obtained by mixing 1 to 20 parts by weight of a thermoplastic resin having a compatibility with a phenol resin at 20 ° C. of 20% or less.

Hereinafter, the present invention will be described in detail. The composite building material referred to in the present invention is an inorganic material composed of an aggregate containing fly ash as an aggregate component and a phenol resin binder.
It is an organic composite building material. 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, fibrous, granular, powdery, lumpy aggregates and reinforcing fibers can be used. For example,
One or two or more kinds of inorganic aggregates such as pumice (volcanic gravel), silica sand, aluminum hydroxide, calcium carbonate, alumina, talc and mica can be used in combination. As the reinforcing fibers, for example, inorganic fibers such as glass fibers, rock wool and 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.

Fly ash must be contained as a part of the aggregate, preferably 20% by weight or more, more preferably 40% by weight or more of the aggregate. By doing so, a lightweight, high-strength composite building material can be obtained.

The phenolic resin used in the phenolic resin binder of the present invention is not limited as long as it is solid at room temperature, and phenols such as phenol, cresol and xylenol are reacted with formaldehyde in the presence of a catalyst. It may be obtained, and examples thereof include novolac type phenol resin, resol type phenol resin, modified phenol resin thereof, and resin mixture thereof. 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.

In the phenol resin binder of the present invention, one or more plasticizers selected from paratoluene sulfonamide, dicyclohexyl phthalate and triphenyl phosphate are added to the above phenol resin. With other plasticizers, the effect of the present invention does not sufficiently occur. The mixing ratio of the plasticizer to the phenol resin is determined from the viewpoint of strength of the molded product, but is 2 to 8 parts by weight, preferably 3 parts by weight with respect to 100 parts by weight of the phenol resin.
７7 parts by weight. In addition, when 2 or more types of plasticizers are mixed, it is a total amount. If the compounding ratio of the plasticizer is less than 2 parts by weight, the effect of improving the strength of the composite building material is not remarkable, and 8
If it exceeds the amount by weight, only the effect as a bulking agent can be expected.

In addition to the phenolic resin and the plasticizer, the phenolic resin binder of the present invention contains a wax having a melt viscosity at 150 ° C. of less than 1 poise and a compatibility with the phenolic resin at 150 ° C. of 5% or less. 1
Melt viscosity at 50 ° C is 150 at 1-1000 poise
A thermoplastic resin having a compatibility with a phenol resin at 20 ° C. of 20% or less or both of them is blended.

The wax used in the present invention has a melt viscosity at 150 ° C. of less than 1 poise and is 150.
Any wax can be used as long as it has a compatibility with the phenol resin at 5 ° C. of 5% or less. Examples of such waxes include natural waxes such as animal and vegetable waxes, mineral waxes and petroleum waxes, and synthetic waxes such as polyethylene waxes and Fischer-Tropsch waxes.

The melt viscosity of wax can be measured by a cone-plate viscometer. Further, the compatibility with the phenol resin is measured by placing an equal mixture of the phenol resin and the wax in a glass container, melt-mixing at 150 ° C., allowing to stand at this temperature for 120 minutes, and then observing the phase state. can do. That is, when the phase becomes one and is transparent, it is completely compatible (100%), and when there are three phases, it is partially compatible and the formula [(intermediate phase volume /
The value of (total volume) × 100] is the percentage (%) indicating the degree of compatibility, and the case where two phases are present as they are or one phase is suspended is regarded as incompatible (0%).

The thermoplastic resin used in the present invention has a melt viscosity at 150 ° C. of 1 to 1000.
Poise, preferably 1-100 poise, 150
Any thermoplastic resin can be used as long as the compatibility with the phenol resin at 20 ° C. is 20% or less, preferably 10% or less. Examples of such a thermoplastic resin include low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene, and hydrocarbon-based oligomers such as coumarone-indene resin, petroleum resin, and terpene resin, or hydrides thereof. To be
Preferred are aromatic hydrocarbon oligomers such as coumarone-indene resin, petroleum resin and terpene resin.

The melt viscosity of the thermoplastic resin can be measured by a cone plate viscometer. Regarding compatibility with phenol resin, 5 g of phenol resin and 5 g of thermoplastic resin are put in a glass container of 20 cc, melt-mixed at 150 ° C., and allowed to stand at this temperature for 120 minutes, and then the state of phase is observed. To measure. When the phase becomes one and is transparent, it is completely compatible (100%), and when three phases are present, it is partially compatible and the formula [(intermediate phase volume / total volume)
The value obtained by quantitatively evaluating the percentage (%) of the value x100], the case where two phases remain as they are or one phase is suspended as incompatibility (0%).

The wax and the thermoplastic resin used in the present invention may be used either individually or in combination of two or more, but in the case of two or more, they are the total amount. The mixing ratio of wax to phenol resin is 100
0.1-5 parts by weight, preferably 0.5-
4 parts by weight. The mixing ratio of the thermoplastic resin to the phenol resin is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the phenol resin. When using both wax and thermoplastic resin together,
The effect can be recognized even if the respective compounding ratios are somewhat reduced.

The method of mixing the phenolic resin with the plasticizer, wax or thermoplastic resin is arbitrary, but each is made into a powder and mixed with powder, a method of pulverizing and mixing with the phenolic resin, a method of melt mixing, There is a method of adding in the reaction or dehydration step of the phenol resin, but the method is not limited to these. In order to bring out the effect of improving the strength with a small mixing ratio, it is preferable to mix them as uniformly as possible, and from this point, the method of melt mixing them is more effective. A method in which the plasticizer is melt-mixed with the phenol resin and the wax or the thermoplastic resin is pulverized and mixed is also effective. Moreover, when manufacturing a composite building material without mixing beforehand, you may add and mix these.

In addition to the plasticizer, wax and / or thermoplastic resin, the phenolic resin binder of the present invention contains
If necessary, various additives such as a curing accelerator, a silane coupling agent, and a lubricant can be added. 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 aggregate containing fly ash as a main component, it is used as a mixture in a solid state, preferably a powder state.

Next, a method for manufacturing the composite building material of the present invention 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.
For example, an aggregate including fly ash and the binder are dry-mixed, a mold is filled with the mixture, a method of heating and pressurizing, the mixture is uniformly sprayed on a caul plate, after forming a laminate, There is a method of heating and pressing, 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 resin composition 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 blending amount is less than 5 parts by weight, the strength as a composite building material is not sufficient, and if it exceeds 20 parts by weight, the flame retardancy decreases, and it is economical to use a large amount of expensive resin compared to the aggregate. Sex is impaired.

As a method of molding the composite building material as described above, a method of heating and pressurizing 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 can be 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.

By molding a molding material in which the phenol resin binder of the present invention and an aggregate containing fly ash are mixed, the mechanical strength of the molded product is improved, and the workability in removing the molded product from the mold is improved. It That is, it can be easily taken out without applying or spraying the mold release agent on the mold or even if the number of times is greatly reduced. The term "improved mechanical strength" as used in the present invention means that the strength obtained when a plasticizer, a wax and / or a thermoplastic resin is not mixed with a phenol resin is standard, and the mechanical strength is improved at a significant level. Further, the term "improved releasability" as used in the present invention means that the releasability obtained when the plasticizer and / or the thermoplastic resin is not added to the phenol resin is taken as a standard and further improved.

[0025]

The present invention will be described below with reference to examples and comparative examples. The following methods were used for evaluation of mechanical strength and releasability.

Evaluation of Mechanical Strength A mold was filled with a dry mixture of 2400 g of fly ash and 360 g of a powdery phenolic resin binder, and the mixture was heated and pressed (160 ° C. × 15 minutes, 20 kg / cm).
² ) Then, an inorganic-organic composite building material of 400 × 400 × 15 mm (hereinafter, abbreviated as board A) is molded, 10 test pieces of 300 × 20 × 15 mm are cut out from the board A, and the span is 250 mm after measuring the density. The bending strength was measured with and the average value and standard deviation were obtained.

Evaluation of releasability A dry mixture of 600 g of fly ash and 90 g of powdered phenol resin binder was thoroughly cleaned in advance and filled in a mold not coated with a mold releasing agent at room temperature, followed by heating and pressurizing (1
60 ℃ × 15 minutes, 20kg / cm ² ), 200 × 2
00x15mm inorganic-organic composite building material (hereinafter, Board B
The mold releasability when the board B is released from the mold was observed. The mold releasability was evaluated by repeating molding 15 times, and ⊚: sufficient releasability was obtained on both upper and lower surfaces,
◯: There was no release resistance on both upper and lower sides, Δ: There was some release resistance on one side, and ×: Releasing property was poor. The number of mold releasability (times) is the number of times of molding from the beginning, and indicates the last molding times when the above evaluation was obtained.

Examples 1 to 8 and Comparative Examples 3 to 5 A predetermined amount of a plasticizer 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. It was solidified after being melt-mixed at 150 ° C. Wax and / or solidified mixture
Alternatively, a predetermined amount of the thermoplastic resin and 15 parts by weight of hexamethylenetetramine as a curing agent were uniformly mixed and then pulverized to prepare a phenol resin binder. The obtained phenol resin-based binder was mixed with fly ash according to the method described above, molded, and evaluated.

Table 1 shows the blending ratio of the phenol resin binder. In addition, these Examples 1-8 and Comparative Example 3-
The plasticizer, wax, and thermoplastic resin used in No. 5 are as follows. A: paratoluene sulfonamide, B: dicyclohexyl phthalate, C: triphenyl phosphate, D: tricresyl phosphate, a: carnauba wax (melt viscosity 0.1 poise or less, compatibility 0%, melting point 83 ° C.),
b: Paraffin wax (melt viscosity of 0.1 poise or less,
Compatibility 0%, melting point 69 ° C., a: coumarone-indene resin (melt viscosity 12 poise, compatibility 5%, softening point 100)
℃), B: Petroleum resin (melt viscosity 90 poise, compatibility 0
%, Softening point 110 ° C.) C: Petroleum resin (melt viscosity 26 poise, compatibility 100%, softening point 95 ° C.)

Comparative Example 1 Molding and evaluation were carried out in the same manner as in Example 1 except that no plasticizer, wax and / or thermoplastic resin was added.

Comparative Example 2 100 parts by weight of a novolac type phenol 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
The phenol resin binder obtained by crushing after addition by weight was mixed with fly ash according to the method described above, molded, and evaluated.

Table 2 shows the evaluation results of the mechanical strength of the board A of the example and the comparative example and the releasability at the time of molding the board B.
The intensity ratios in Table 2 are shown with Comparative Example 1 as 100.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

Industrial Applicability According to the method for producing a composite building material of the present invention, the mechanical strength is significantly improved at a significant level as compared with the prior art method for producing a composite building material, and excellent releasability is obtained at the time of molding. It can be exhibited, the defect rate can be significantly reduced, and the workability can be improved and the cost can be reduced.

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Claims (1)

[Claims] 1. In manufacturing a composite building material by binding and curing an aggregate containing fly ash with a phenol resin binder, p-toluenesulfonamide, dicyclohexyl phthalate and triphenyl phosphate are added to 100 parts by weight of a solid phenol resin. A wax having a melt viscosity at 150 ° C. of less than 1 poise and a compatibility with the phenol resin at 150 ° C. of 5% or less and 0.1 to 5 parts by weight of 2 to 8 parts by weight of one or more plasticizers selected from
1 to 10 parts by weight and / or melt viscosity at 150 ° C.
A method for producing a composite building material, which comprises using 1 to 20 parts by weight of a thermoplastic resin having a compatibility of 20% or less with a phenol resin at 150 poise at 00 poise.