JPH1025145A - Composition for molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for molding a building material which is less deformable even under extremely high temperature conditions such as fire, has crack resistance and shape retention, and is excellent in fire resistance. A composition comprising 25 parts by weight of a thermoplastic resin, 5 to 50 parts by weight of a phenolic resin, and 30 to 230 parts by weight of calcium silicate, wherein the composition contains inorganic fibers and an impact-resistant material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a molding composition. More specifically, the present invention relates to a molding composition having excellent fire resistance, particularly excellent crack resistance and shape retention during combustion, and suitable for building materials such as window frames, doors, and wall materials.

[0002]

2. Description of the Related Art Resin-based materials have excellent moldability and are widely used as materials for obtaining molded articles of various shapes. However, many resin-based materials are flammable, and have poor fire resistance, such as shape deformation due to combustion and cracking due to loss of resin components, and their use in the construction field is considerably limited.

[0003] Conventionally, as one of measures for improving fire resistance, compounding with an inorganic material has been known. However, in order to maintain the properties of resin such as heat insulation and easy moldability, the addition rate of the inorganic material is limited. It was rather limited, and it was difficult to obtain a molded article having excellent fire resistance, particularly excellent shape retention during and after combustion. That is, cracking due to remarkable volume shrinkage occurs due to the softening or disappearance of the resin at a high temperature, and it has been difficult to obtain a molded body that retains its shape after burning.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to have properties of a resin such as heat insulating property and easy moldability, and to be excellent in fire protection property, especially in shape retention during and after combustion, and can be widely used as a building material. An object of the present invention is to provide a molding composition.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, a molded product of a composition comprising a thermoplastic resin, a phenolic resin and calcium silicate was obtained at a high temperature. The present inventors have found that the present invention has excellent fireproofing properties, such as suppressing the generation of cracks when the resin disappears in the above process, or having the sealing properties of the generated cracks, and further research has led to the completion of the present invention.

That is, the present invention provides a molding composition comprising 25 parts by weight of a thermoplastic resin, 5 to 50 parts by weight of a phenolic resin, and 30 to 230 parts by weight of calcium silicate.
It is. Hereinafter, the present invention will be described in detail. As the thermoplastic resin applied to the present invention, polyvinyl chloride, polyvinyl acetate, polypropylene, olefin resin such as polyethylene, styrene resin, acrylic resin such as polymethyl methacrylate, polyamide resin such as nylon, polycarbonate, polyethylene terephthalate and the like And polyether resins such as polyacetal and polyphenylene ether, polysulfone, polyvinyl alcohol, and polyacrylonitrile. These may be used alone, or two or more of them may be used as a mixture or as a copolymer.

Among them, polyvinyl chloride, nylon, polyphenylene ether, polyethylene terephthalate, and polysulfone, which have a relatively high softening temperature of the resin, are preferable. Further, considering the flame retardancy of the resin itself, vinyl chloride resin and vinyl chloride are preferred. Vinyl chloride resins such as polymers are preferred. The thermoplastic resin used in the present invention is preferably a homopolymer or a copolymer having an average degree of polymerization of 600 to 4000,
Additives such as stabilizers, lubricants, impact modifiers, and flame retardants may be included.

[0008] Examples of the phenolic resin applicable to the present invention include a resol resin and a novolak resin.
These can be used alone or in combination of two or more. A material that does not thermoset at the softening temperature of the thermoplastic resin is desirable from the viewpoint of moldability of the phenolic resin, and it is preferable to use a novolak resin having an average degree of polymerization of 800 to 900 without adding a curing agent.

The calcium silicate used in the present invention includes:
Specific examples include crystalline calcium silicate hydrates such as zonotolite and tobermorite, calcium silicate hydrates having relatively low crystallinity called CSH-I and CSH-II, and wollastonite. These can be used alone or as a mixture of two or more kinds. However, the primary particles have an aspect ratio of 5 to 500, that is, a fibrous or acicular shape, and they are entangled. It is preferable to form a bulky higher-order structure including voids inside, and it is particularly preferable to use zonotolite.

The inorganic fibers applicable to the present invention include glass fibers, carbon fibers, rock wool and the like. In particular, glass fibers having a length of 12 mm or less and a diameter of 5 to 25 μm are preferable. The inorganic fiber used in the present invention has a resin content of 3% in consideration of the moldability and heat insulation of the molded product.
It is preferably 0% by weight or less. When the inorganic fiber is contained, the strength of the molding material is improved, and the material shrinkage during combustion is reduced.

The composition of the present invention requires 5 to 50 parts by weight of a phenolic resin and 30 to 230 parts by weight of calcium silicate based on 25 parts by weight of a thermoplastic resin. 10 to 25 parts by weight of phenolic resin, 30 parts by weight of calcium silicate, based on 25 parts by weight of plastic resin
To 50 parts by weight, more preferably 20 to 25 parts by weight of a phenolic resin and 40 to 50 parts by weight of calcium silicate based on 25 parts by weight of a thermoplastic resin.

In the molding composition of the present invention, the ratio of the resin component is preferably in the range of 11 to 71% by weight,
When the amount is less than 11% by weight, a molded article having characteristics of a resin such as low water absorption and high toughness cannot be obtained, and the resin component has a content of 7%.
If it is more than 1% by weight, it is not possible to obtain a fireproof material. The molded article made of the molding composition of the present invention is excellent in fire resistance, because the resin component is melted while the shape is maintained by the inorganic material calcium silicate at a high temperature, and the thermoplastic resin burns out. In the meantime, the volume is expanded by foaming due to the cyclocondensation reaction of the aromatic ring portion of the phenol resin, and a heat insulating layer that blocks oxygen during combustion accompanying the progress of carbonization is formed, and combustion is suppressed. , Is considered to suppress the generation of cracks in the composition or to close the generated cracks.

[0013] Such an effect is required when a phenol resin, especially a novolak resin, is at least 5 parts by weight based on 25 parts by weight of a thermoplastic resin and 30 to 230 parts by weight of calcium silicate. Considering the moldability of the composition as well as the fire protection, the phenolic resin needs to be 5 to 50 parts by weight. A molded article using the molding composition of the present invention was extruded or injection-molded, and a long one, a flat plate having a large area, and even a thin building member were burned under high-temperature conditions such as a fire. Even in this case, no flow of resin is seen,
There is little warping and bending, and cracks are hardly generated. Even if cracks are generated, the shape can be maintained without penetrating. Therefore, there is no leakage of smoke to the back side of the combustion surface.

The molding composition of the present invention is a composition that can be molded by various molding methods. Examples of the molding method include a press molding method, an extrusion molding method, a calendar molding method, and an injection molding method. In order to produce a molded article by the molding method described above, it is preferable to mix the composition so that the resin, the inorganic material, the inorganic fibers, and the like are uniformly dispersed. Mixing can be performed using a conventional mixer such as a universal mixer, a kneader, a blender, or a roll.

A molded article using the molding composition of the present invention can be used for a wide range of building materials such as window frames, wall materials, doors, flooring materials, and other fire-resistant building members, building components, and furniture. Applicable to

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, the raw materials used and the evaluation method are shown below. (1) Vinyl chloride resin As a result of measuring the particle size distribution using a laser light scattering type particle size distribution measuring apparatus, 100% of particles having a particle size of 10 to 100 μm are 100%.
Powder (trade name: EX-20, manufactured by Shin-Etsu Polymer Co., Ltd.)
6) was used. (2) Vinyl chloride-acrylic copolymer emulsion Water-based emulsion having a resin content of 50% and a minimum film-forming temperature of 100 ° C. (trade name: VINIBLAN 60, manufactured by Nissin Chemical Industry Co., Ltd.)
9). (3) Novolak resin powder As a result of measuring the particle size distribution using a laser light scattering type particle size distribution measuring apparatus, 100% of particles having a particle size of 10 to 100 μm were obtained.
(AKK-1 manufactured by Asahi Organic Materials Co., Ltd.) was used. (4) Zonotorite Observed with a SEM, a powder was used in which it was confirmed that the primary particles had an aspect ratio of 10 or more, and that they were entangled to form secondary particles having a particle size in the range of 20 to 40 μm. Was. (5) Glass fiber 3 m length of glass fiber surface treated with silane compound
m, glass fiber having a diameter of 13 μm (chopped strand, manufactured by Nitto Boseki Co., Ltd.). (6) Fireproof test Using a building material flammability test device (manufactured by Toyo Seiki Seisakusho Co., Ltd.), it was rated as the first class of flame retardancy in the surface test of flammability test method (JIS A1321) for building interior materials and construction methods. According to
A 220 × 220 × 5 mm plate-shaped specimen is heated, and the deformed state of the appearance of the specimen after heating, such as warpage and cracks, is evaluated as follows: ：: no warping and cracking by heating; Less occurrence, no crack reaching the heated back surface, Δ: Little occurrence of warpage due to heating, but cracks reaching the heated back surface, ×: Extremely warped due to heating, generation of cracks that split the test specimen into multiple parts. It was rated on a scale.

[0017]

Example 1 Vinyl chloride resin powder 2 as a thermoplastic resin
5 parts by weight, 25 parts by weight of novolak resin powder as a phenolic resin, and 50 parts by weight of zonotolite as calcium silicate, all-purpose mixer manufactured by Kodaira Seisakusho Co., Ltd., trade name, A
Using CM-30L５, the mixture was mixed at 110 rpm for 5 minutes to make it uniform. This mixture was extruded using a single-screw extruder {ONP-50B} (manufactured by Kodaira Seisakusho Co., Ltd.) while being melt-kneaded in a temperature range of 170 ° C. to 190 ° C. and a screw rotation speed of 30 rpm. A flat plate having a thickness of 240 mm and a thickness of 5 mm was obtained. 2 from this flat plate
A sample of 20 mm × 220 mm was taken and subjected to a fire resistance test. Table 1 shows the results of the fire resistance test.

[0018]

Example 2 50 parts by weight of a vinyl chloride-acrylic copolymer emulsion (resin content 25 parts by weight) as a thermoplastic resin, and novolak resin powder 25 as a phenolic resin
Parts by weight, 45 parts by weight of zonotrite as calcium silicate, glass fiber (length 3 mm, diameter 12 μm) as inorganic fiber
m) was mixed with 10% of the resin component in the same manner as in Example 1 to make the mixture uniform, and then allowed to stand at room temperature for one day and dried. A flat plate was extruded from the mixed raw material after drying in the same manner as in Example 1. Table 1 shows the results of the fire protection test performed on this flat plate.

[0019]

Comparative Example 1 A flat plate was extruded in the same manner as in Example 1 except that novolak resin powder was not used, with 50 parts by weight of vinyl chloride resin powder and 50 parts by weight of zonotolite. Table 1 shows the results of the fire protection test performed on this flat plate.

[0020]

COMPARATIVE EXAMPLE 2 A flat plate was extruded in the same manner as in Example 1 except that 50 parts by weight of a vinyl chloride resin powder, 50 parts by weight of a novolak resin powder and zonotlite were not used. Table 1 shows the results of the fire protection test performed on this flat plate.

[0021]

Comparative Example 3 A flat plate was extruded in the same manner as in Example 1 except that no thermoplastic resin was used and 50 parts by weight of novolak resin powder and 50 parts by weight of zonotolite were used. Table 1 shows the results of the fire protection test performed on this flat plate.

[0022]

[Table 1]

[0023]

The molding composition of the present invention has less deformation, crack resistance and shape retention even when burned under extremely high temperature conditions such as fire, as compared with conventional resin compositions. In addition, a molded article such as a window frame, a wall material, a door, and a floor material having excellent fire resistance can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C04B 14:42 14:38 14:46) 111: 28

Claims (4)

[Claims] 1. 25 parts by weight of a thermoplastic resin, 5 to 50 parts by weight of a phenolic resin, 30 to 230 parts of calcium silicate
A molding composition comprising parts by weight. 2. The molding composition according to claim 1, wherein the thermoplastic resin is a vinyl chloride resin. 3. The molding composition according to claim 1, wherein the inorganic fibers are blended in an amount of 30% by weight or less based on the components of the thermoplastic resin and the phenolic resin. 4. The molding composition according to claim 3, wherein the inorganic fibers are at least one selected from glass fibers, carbon fibers, and rock wool.