JPH0586260A - Molding material and molded article - Google Patents

Abstract

PURPOSE:To obtain a molding material providing molded articles having excellent bond strength and flame retardancy, comprising a thermosetting resin and a fibrous base subjected to surface treatment with a thermosetting resin. CONSTITUTION:The objective molding material comprises (A) a thermosetting resin composed of a high ortho-novolak type phenol resin preferably containing a large amount of hexamethylenetetramine as a curing agent and (B) a fibrous base composed of preferably glass fibers subjected to surface treatment with a thermosetting resin composed of preferably phenol resin as essential components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material excellent in mechanical strength and a molded product obtained from the molding material.

[0002]

2. Description of the Related Art As a non-combustible material excellent in flame retardancy and water resistance and an exterior material, a mixture of a novolac type phenol resin and hexamethylene tetramine is used as a binder, and a fibrous base material is used as a reinforcing material. It is known that this is heat-cured and molded.

[0003]

However, when the conventional fibrous base material is used, the mechanical strength of the molded product obtained by thermosetting is insufficient.

[0004]

The inventors of the present invention have made diligent studies in view of the above-mentioned circumstances, and as a fibrous base material, a thermosetting resin of the same type or a thermosetting resin as a binder is used. When a fibrous base material that is surface-treated with a thermosetting resin with excellent adhesiveness is used, the mechanical strength of the molded product obtained by thermosetting is the same as conventional molding using a fibrous base material that does not have any surface treatment. It was found that the size of the molded product obtained from the material was extremely larger than that of the molded product, and the present invention was completed.

That is, the present invention uses a fibrous base material surface-treated with a thermosetting resin as the fibrous base material in a molding material containing a thermosetting resin and a fibrous base material as essential components. And a molded product obtained by thermosetting the molding material.

In the present invention, as the thermosetting resin used as the binder, any known and commonly used thermosetting resin can be used. For example, formaldehyde resins such as urea resin, melamine resin, and phenol resin, epoxy resin, urethane resin, unsaturated polyester resin, and the like.

For example, a melamine resin may be used in combination with a curing agent such as sulfuric acid or an organic sulfonic acid, and a novolac type phenol resin may be used in combination with a curing agent such as hexamethylenetetramine or divinylbenzene. The epoxy resin may be used in combination with a curing agent such as acid anhydride, polyamine, polyamide resin and novolac type phenol resin. The resol type phenol resin can be used as it is.

For a molding material using an inorganic aggregate characterized by being flame-retardant, it is preferable to use a phenol resin whose binder itself is flame-retardant. The phenolic resin may be liquid or powder, and may be novolac type or resol type, but a resin of fast curing design is preferable in order to shorten the compression molding time, and powdered novolac type is hexamethylenetetramine as a curing agent. Those containing a large amount of are preferable.

As the novolac type phenol resin according to the present invention, any known and conventional one can be used. Among them, the high ortho novolac type phenolic resin is preferable to the conventional novolac type phenolic resin in that the curing speed is high.

The novolac type phenol resin can be easily prepared by reacting a formaldehyde supply substance and a phenol with a molar ratio of 0.7 to 1.0, if necessary, in the presence of a catalyst. You can get it.

As the phenols used in the present invention, any of the known and conventional ones can be used. For example, phenol, bisphenols such as bisphenol F, bisphenol A and bisphenol AF, cresol,
Alkyl-substituted phenols such as P-tertiarybutylphenol, halogenophenols such as bromophenol, aromatic hydrocarbons containing two or more phenolic hydroxyl groups such as resorcin, 1 naphthol, 2 naphthol, 1,6-dihydroxynaphthalene, Examples include naphthols such as 2,7-dihydroxynaphthalene. These phenols may be used alone or in combination of two or more kinds.

As the formaldehyde supplying substance, any known substance can be used, for example, an aqueous formaldehyde solution or paraformaldehyde can be used. Examples of the catalyst include acid catalysts such as oxalic acid, hydrochloric acid and sulfuric acid, and metal salt catalysts such as zinc acetate and manganese borate.
When the metal salt catalyst is used, a high ortho novolac type phenol resin can be obtained.

In producing the novolac type phenolic resin, furfural, urea, melamine, acetoguanamine, benzoguanamine and the like may be used in combination with the phenols, if necessary.

The above reaction may be carried out in the presence of an organic solvent, or a solvent may be added to the obtained reaction product. The above reaction may be carried out in a batch kettle or in a tubular reactor with a static mixer.

Usually, when a novolac type phenol resin is used in the present invention, it is preferable to use a powdered one. When the novolac type phenol resin is in the form of an aqueous solution, a water dispersion liquid, or an organic solvent liquid, it is preferable to remove the solvent, dry and pulverize before use. When the solvent is removed and the drying is performed, for example, a thin film evaporator or a spray dryer can be used.

In the present invention, the mixing ratio of the novolac type phenol resin and hexamethylenetetramine is not particularly limited, but usually 5 to 25 hexamethylenetetramine per 100 parts by weight of the solid content of the novolac type phenol resin. Parts by weight.

Examples of the fibrous base material include glass fiber,
Inorganic fibrous base materials such as carbon fiber and silicon carbide fiber, phenol resin fiber, aramid resin fiber, polyarylene sulfide resin fiber, nylon fiber and the like can be mentioned, but the strength of the resulting molded product is excellent and the economy is also excellent. In view of this, glass fiber is preferable.

The form of the fibrous base material is not particularly limited and includes, for example, chopped strand, chop mat, chop cloth, roving, roving cloth,
Examples include non-woven fabrics.

The present invention is characterized in that the fibrous base material is surface-treated with a thermosetting resin. As the thermosetting resin for treating the fibrous base material,
For example, any of the above-mentioned binders can be used, and examples thereof include urea resin, phenol resin, melamine resin, epoxy resin, urethane resin and the like.

At this time, if the thermosetting resin used as the binder and the thermosetting resin for surface-treating the fibrous base material have the same or similar structure, the adhesive strength between them can be further improved. You can

When a phenolic resin is used as the binder for the molding material, epoxy resin, urethane resin, etc. are equivalent to or more than the phenolic resin and can be used only from the viewpoint of adhesiveness. Phenolic resin is preferable in terms of excellent adhesiveness and heat resistance. The phenol resin used may be a novolac type phenol resin, a resol type phenol resin, or a mixture of both.

As a method for treating the fibrous base material, any known and commonly used method can be adopted, but, for example, an impregnation method or a spray method is general. The state of the resin on the fibrous base material surface-treated with the thermosetting resin is not particularly limited, and is usually a semi-cured state (B stage state) excluding volatile components,
Although it can be used in either a completely cured state (C stage state), the B stage state is superior in terms of adhesiveness with a binder or the like.

The larger the amount of the thermosetting resin adhered to the fibrous base material, the more preferable.
The range of 50 to 100 parts by weight is preferable.

Further, the strength of a molded product obtained by further combining a thermosetting resin used as a binder or a thermosetting resin for treating a fibrous base material with a coupling agent such as a silane type or a titanate type in advance is further improved. It can be done.

The fibrous base material surface-treated with the thermosetting resin may be separately produced from the untreated fibrous base material by the above-mentioned operation and used, but from the viewpoint of recycling. It is also possible to use scraps of the fibrous base material in the B-staged state which has been impregnated with the phenol resin, melamine resin, epoxy resin, urethane resin, etc. and dried. Examples thereof include glass fibers impregnated with a phenol resin and dried, for example, chopped punching scraps of a glass cloth prepreg used as a reinforcing material when manufacturing a grindstone.

The molding material of the present invention may contain a thermosetting resin and a fibrous base material surface-treated with the thermosetting resin as essential components, but an inorganic aggregate can be used in combination. Examples of the inorganic aggregate include magnesia, alumina, calcium carbonate, magnesium carbonate, volcanic ash, volcanic gravel, fly ash, and the like, but from the viewpoint of economy, volcanic ash, volcanic gravel, and fly ash are preferable.

The particle size of the inorganic aggregate is not particularly limited, but is preferably about 0.001 to 6 mm. If inorganic aggregates having different particle diameters are used in combination and the proportion thereof is adjusted as necessary, it is possible to obtain a light-weight and strong molded product.

The molding material of the present invention is filled with a thermosetting resin, a fibrous fiber previously treated with a thermosetting resin, and if necessary, an inorganic aggregate in a mold of a predetermined shape and cured by thermoforming. You can get it easily.

The conditions for thermoforming are not particularly limited, but usually 130 ° C. to 250 ° C. and 3 to 60 minutes. Although the pressure depends on the density of the target molded product, it is usually 1
It is 0 to 100 kg / cm ² .

Next, an example of the method for producing the molding material of the present invention will be described. (1) First, a mixture of a thermosetting resin and an inorganic aggregate is sprinkled on a stainless steel plate. (2) Next, a fibrous base material surface-treated with a thermosetting resin is placed thereon. (3) Further, a mixture of the inorganic aggregate and the thermosetting resin is sprayed. (4) Place the same fibrous base material as used in (2) above,
Then, the mixture used in (1) above is sprinkled to form a sandwich, which is hot-pressed to have a predetermined thickness.

[0031]

EXAMPLES The present invention will be described below with reference to examples, but "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified. Example 1 Novolac-type phenol resin powder containing 15 parts of hexamethylenetetramine [melting point: 80 ° C. (capillary method), gelation time: 65 seconds (150 ° C. on hot plate, stroke cure), fluidity 3
5 mm (125 ° C, 25 ° C on a tilted glass plate),] 100
Parts were used as binders. (1) A fly ash having a diameter of 0.01 to 0.1 mm was used as the inorganic bone agent, and 100 kg of the fly ash was mixed well with 15 parts of the above powdered phenol resin (hereinafter referred to as mixture A) to be 1.5 kg / m ^2. Was evenly dispersed on a stainless plate. (2) Next, glass chopped strand ECS 9-
3 (JIS R 3419), a methanol solution of a resol-type phenol resin [solid content 60%, viscosity 150 (cps / cps /
25 ° C.)] to 100 parts of glass chopped strands by spray coating so as to have a resin solid content of 50%, and dried at 80 ° C. for 10 minutes to obtain glass fibers surface-treated with a phenol resin (this). As coating chop B.). The state of the phenol resin on the glass fiber after the surface treatment was B-state.

0.2 kg of this coating chop B
The mixture was evenly sprayed on the mixture A at a ratio of / m ² . (3) Then, a mixture of 100 parts of the same mixture A as 100 parts of the volcanic rubble adjusted to a diameter of 2 mm to 6 mm was mixed well on this, and uniformly mixed at a rate of 5.0 kg / m ^2. Sprayed.

(4) Further, the above coating chop B was evenly dispersed on this at a rate of 0.2 kg / m ² . (5) Finally, the same amount as the mixture A was uniformly sprayed in the same amount as in (1). The sandwich-like material produced in this manner is pressed to a thickness of 15 mm and the temperature is set to 180.
Molded at 15 ° C for 15 minutes. Then, it was cured at 120 ° C. for 16 hours to obtain a final product. The bulk specific gravity of this molded product is 0.80
Met.

The normal bending strength of the molded product is that the width of the molded product is 25 m.
m, span 150 mm, and head load speed 10 mm / min. were measured using a universal tester manufactured by Orientec Co., Ltd. Water resistance bending strength is 2 in water at room temperature (20 ℃)
It was immersed for 4 hours, and the measurement was performed under the same conditions as described above in the wet state. The results are shown in Table 1. Comparative Example 1 A molded plate was obtained in exactly the same manner as in Example 1 except that the glass chopped strand used in Example 1 had no treatment. The strength was measured in the same manner. The results are shown in Table 1. Example 2 In Example 1, a methanol solution of a resol-type phenol resin containing γ-aminopropyltriethoxysilane (silane coupling agent) at a ratio of 0.5 parts per 100 parts of resin solid content was used. A molded plate was produced under exactly the same conditions as in Example 1 except that a coating chop which was surface-treated by the same operation using the same material as the others was used.

The obtained molded plate had a bulk specific gravity of 0.80 and a thickness of 15 mm. The strength is measured in the same manner as in Example 1, and the results are shown in Table 1. Example 3 Glass roving cloth ERC 58 as a fibrous base material
0 (JIS R 3417), a mixture of novolac resin and resol resin in a solid content of 6/4 [solvent
Methanol, nonvolatile content 55 (%), viscosity 100 (cps / 2
5 ° C.)] as a thermosetting resin for surface treatment, 40% of the resin mixture solid content was adhered to 100 parts by weight of a roving cloth, dried, and cut into a diameter of 3 to 5 cm.

Other conditions were the same as in Example 1 to obtain a molded plate having a bulk specific gravity of 0.80 and a thickness of 15 mm. The results of measuring the strength under the same conditions as in Example 1 are shown in Table 1.

[0037]

[Table 1] As can be seen from Table 1, the molded product of the molding material obtained by using the fibrous base material surface-treated with the thermosetting resin is superior to the molded product of the molding material obtained by using the untreated fibrous base material. It is clear that the strength is remarkably improved.

[0038]

The molding material of the present invention and the molded product obtained by curing the same are not untreated as fibrous base materials,
Since a surface-treated product with a thermosetting resin is used, there is a particularly remarkable effect that a molded product having significantly higher mechanical strength can be obtained as compared with a molded product of a conventional molding material.

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Claims (5)

[Claims] 1. A molding material containing a thermosetting resin and a fibrous base material as essential components, wherein a fibrous base material surface-treated with a thermosetting resin is used as the fibrous base material. Molding material to be used. 2. The molding material according to claim 1, wherein the thermosetting resin and the thermosetting resin obtained by surface-treating the fibrous base material are the same. 3. The molding material according to claim 1, wherein both the thermosetting resin and the thermosetting resin obtained by surface-treating the fibrous base material are phenolic resins. 4. The molding material according to claim 1, which further contains an inorganic aggregate. 5. A molded product obtained by thermosetting the molding material according to claim 1.