JPS6248707B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to flame retardant compositions. More specifically, the present invention relates to a flame-retardant composition comprising a resin-based material and a cellulose-based flame-retardant filler formed by chemically bonding or fixing condensed ammonium phosphate to a cellulose-based material. Traditionally, cellulose-based materials such as wood flour and pulp have been used as fillers and mixed with resin-based materials to create lightweight, resource-saving, improved sound-absorbing and heat-insulating properties, or composite materials that have been made into a pseudo-wood material. It has been commercialized. However, when these composite materials are viewed as building materials or general molding materials, their flame retardant performance cannot be ignored in their evaluation. Recently, much research and development has been carried out on flame retardant resin base materials or flame retardant composite materials by using flame retardants as fillers. As a result of intensive research into the development of flame-retardant composite materials, the present inventors discovered that combustible cellulose-based materials can be made flame-retardant by chemically bonding or fixing condensed ammonium phosphate to cellulose-based materials. As a result of further studies based on this knowledge, we discovered that a flame-retardant composite composition could be obtained by adding and mixing this flame-retardant cellulose material as a filler to a resin-based material.
We have now completed the present invention. That is, the present invention is a flame-retardant composition characterized in that a resin-based material is blended with a cellulose-based flame-retardant filler formed by chemically bonding or fixing condensed ammonium phosphate to a cellulose-based material. , housing equipment parts, building materials, fitting materials, vehicle parts, electrical parts, aircraft parts, etc., obtained by mold-casting such compositions using molding machines such as press molding, injection molding, extrusion molding, and vacuum forming. When molded into parts for ships, etc., it extremely reduces combustibility, making it extremely useful as a composite material. As mentioned above, the cellulose-based flame retardant filler used in the present invention is chemically bonded or fixed (meaning that the combed material hardens in a sticky form) to the cellulose-based material.
The manufacturing method is, for example, impregnating a cellulose material by immersing or spraying it in a condensed ammonium phosphate aqueous solution under normal pressure, reduced pressure, or reduced pressure-pressure.
Dry at a temperature of 300°C, preferably 100-250°C for 1-30 minutes, preferably 1-10 minutes, and
1 to 1 at a temperature of 130 to 300℃, preferably 150 to 250℃
It is manufactured by heating and curing for 10 minutes, preferably 1 to 5 minutes. The heating cure temperature of cellulose material is
When the temperature is higher than 300°C, carbonization of the cellulose material occurs, which deteriorates the quality of the flame retardant filler of the present invention, and when it is lower than 130°C, the esterification reaction between the cellulose material and condensed ammonium phosphate occurs. is not produced, and the adhesion of the condensed ammonium phosphate to the cellulose becomes incomplete, both of which are unfavorable. The heating cure time also depends on the heating temperature, but if it is longer than 10 minutes, esterification of the cellulose-based material with condensed ammonium phosphate will proceed to an extreme extent and cellulose fibers will begin to decompose, and if it is shorter than 1 minute. In this case, there is little esterification of cellulose-based materials, so when mixed with resin-based materials, the condensed ammonium phosphate, which is a flame retardant, falls off from the cellulose materials.
Both of these are unfavorable, since the physical properties of the composition will deteriorate. The chemical bonding of condensed ammonium phosphate to cellulosic materials is e.g. It is caused by a reaction like this. Examples of cellulosic substances used in the present invention include wood flour, wood chips, pulp chips, cotton fibers,
Examples include rayon fiber, whose particle size is 1 to 300.
mesh, fiber length 0.1-10mm, preferably particle size 10
~200 meshes and fiber lengths in the range of 0.5 to 7 mm are used. There is no particular problem when the particle size of the cellulose material is larger than 1 mesh and the fiber length is larger than 10 mm, but it is necessary to crush it in a crusher after flame retardant treatment. If it is smaller than 0.1 mm, it tends to scatter during impregnation, resulting in poor workability, and it also tends to scatter even after flame retardant treatment, both of which are unfavorable. The condensed ammonium phosphate used in the present invention includes:

[Formula] The degree of condensation is 1 to 100, preferably 1 to 60, and the concentration is 1.
~50% (weight%, the same applies hereinafter), preferably 5 to 40
% aqueous solution is employed, whereby the cellulosic material is impregnated with an aqueous solution of condensed ammonium phosphate to bring the condensed ammonium phosphate into contact with the fiber molecules of the cellulosic material, and further dried to remove moisture, and By heating and curing, the hydroxyl groups of the cellulose molecules in contact with the condensed ammonium phosphate are dehydrated, and the condensed ammonium phosphate bonds with the cellulose to phosphoric acid esterify the cellulose and fix the condensed ammonium phosphate to the cellulose. Ru. If the degree of condensation of condensed ammonium phosphate and the concentration of its aqueous solution are outside the above range, condensed ammonium phosphate will be difficult to dissolve in water and will be difficult to uniformly impregnate inside cellulose, and the flame retardant cellulose material will become difficult to dissolve. This is not preferable because the fuel performance and physical properties deteriorate. As the cellulose-based flame retardant filler used in the present invention, the amount of active ingredient of condensed ammonium phosphate contained in the cellulose-based material is 100% of that of the cellulose-based material.
(parts by weight, hereinafter the same) is employed in the range of 5 to 40 parts, preferably 10 to 30 parts, so that when these cellulose-based flame retardant fillers are mixed with resin-based substances, the Good performance in flame retardant performance and physical properties of the composite composition can be exhibited. When the amount of active ingredient in condensed ammonium phosphate is more than 40 parts, flame retardancy cannot be improved so much in proportion to the increase in the amount of active ingredient, making it uneconomical, and when it is less than 5 parts, flame retardancy is imparted. Both are undesirable. The cellulose-based flame retardant filler obtained in this way is used after being finely pulverized if necessary, and pulverization equipment such as a hammer mill type, feather mill type, disk refiner type, or pin mill type is usually used for pulverization. It is crushed into about 100 to 500 meshes, blended with resin-based materials, and used for desired purposes. Examples of resin-based substances used in the present invention include general-purpose thermoplastic resins, thermosetting resins, and monomers and oligomers forming these resins. Examples of thermoplastic resins include polystyrene resin, polyvinyl chloride resin, polyethylene resin, polypropylene resin, polyisobutylene resin, polyacetal resin, polyamide resin, polycarbonate resin, methacrylic resin, polyphenylene sulfide resin, polybutylene terephthalate resin, and phenoxy. Resin, vinyl acetate resin, vinylidene chloride resin, ABS resin, MBS resin, AS resin, AAS resin, or styrene monomer, styrene oligomer, acrylate monomer, acrylate oligomer, etc. are used as appropriate. Examples of thermosetting resins include guanamine resin, diallyl phthalate resin, phenol resin,
Unsaturated polyester resin, furan resin, polyurethane resin, melamine resin, urea resin, epoxy resin, etc. are used as appropriate. The method of blending the cellulose-based flame retardant filler with the resinous material includes, for example, mixing the filler and the resinous material on a heated roll, or adding the cellulose-based flame retardant filler to a solution of the resinous material in which the resinous material is dissolved. A method is adopted in which the filler is immersed for impregnation treatment and the solvent is removed by drying, thereby obtaining a flame-retardant composition in which the filler and the resinous substance are integrated. When using styrene monomer or acrylate monomer as a resin material component, the cellulose-based flame retardant filler is impregnated with the required amount of the monomer to which a polymerization catalyst is added if necessary, and then the filler is heated or irradiated. The filler and resin material are integrated by polymerizing the impregnating monomer or by graft polymerizing with cellulose. In addition, when using styrene oligomer or acrylate oligomer, the viscosity of the oligomer is adjusted with the same type of monomer or solvent as the oligomer depending on the difficulty of impregnating the filler, and the filler and resin are impregnated and polymerized in the same manner as described above. The system substances are integrated. In the flame retardant composition of the present invention, the blending ratio of the resin material and the cellulose flame retardant filler is preferably 30 to 600 parts of the cellulose flame retardant filler per 100 parts of the resin material. is employed in a range of 50 to 500 parts, thereby obtaining a composition that has good flame retardant performance, molding performance, and molded product physical properties as a composite composition. When the amount of cellulose-based flame retardant filler is more than 600 parts, it is impossible to mold it into a composite composition, and when it is less than 30 parts, the flame retardant effect of the resulting composition is insufficient. Undesirable. Therefore, the flame retardant composition of the present invention can be used for housing equipment parts, building materials, fitting materials, vehicle parts, etc., which can be obtained using molding machines such as mold casting, press molding, injection molding, extrusion molding, and vacuum forming. It is used in electrical parts, aircraft parts, ship parts, etc., and is extremely useful as a flame-retardant composite material. Next, the composition of the present invention will be specifically explained with reference to Examples and Reference Examples, but the present invention is not limited only to these Examples. Reference example 1 100 kg of wood flour (10 to 50 mesh) was put into an impregnation tank, and condensed ammonium phosphate (condensation degree 10) was added to the impregnation tank.
~40, product name FR-30, manufactured by Otsuka Chemical Co., Ltd.) 10
% aqueous solution was added and immersed for 30 minutes while stirring. This impregnated wood flour was dehydrated using a dehydrator to achieve an impregnation rate of 60%. This is done using a kiln dryer.
It was dried at 200°C for 2 minutes. The dried wood flour was then cured by heating at 200°C for 2 minutes using a kiln-type heating furnace to obtain flame-retardant wood flour. Reference Example 2 100 kg of pulp chips (fiber length: 1.5 to 2.0 mm) was put into an impregnating tank, and a 20% aqueous solution of condensed ammonium phosphate (same as that used in Reference Example 1) was poured into it, and the mixture was stirred while stirring. Soaked for 10 minutes. The impregnated pulp chips are dehydrated in a dehydrator to determine the impregnation rate.
It was set at 50%. This is dried using a kiln dryer.
It was dried at ℃ for 5 minutes. The dried pulp chips were then heat-cured at 250° C. for 1 minute using a kiln-type heating furnace to obtain flame-retardant pulp chips. Reference example 3 Cotton linter (fiber length: 3-7mm) 100Kg
was placed in an impregnating tank, and a 40% aqueous solution of condensed ammonium phosphate (same as that used in Reference Example 1) was added thereto, and left to impregnate under normal pressure. After being impregnated for 20 minutes, the liquid was removed using a squeezing roll to obtain an impregnation rate of 50%. This is done using a kiln heater.
It was dried at 200°C for 5 minutes. The dried cotton linters were then cured by heating at 200° C. for 3 minutes using a kiln heating furnace to obtain flame-retardant cotton linters. Reference Example 4 A flame-retardant rayon fiber was obtained in the same manner as Reference Example 3 except that rayon fiber (fiber length: 3 to 5 mm) was used. Example 1 10 kg of flame retardant wood flour obtained in Reference Example 1 was uniformly impregnated and mixed with 3 kg of methyl methacrylate monomer (added with 1% azobisisobutyronitrile as a polymerization catalyst) under normal pressure. The mixture was placed in a pressure-tight sealed cell and polymerized by heating at 90°C for 60 minutes. After polymerization, this flame retardant composition is ground into 100 mesh pieces using a grinder, and this powdery composition is made using a heated press.
A board was obtained by press molding at 50Kg/cm ² and 130°C for 3 minutes. Table 1 shows the physical properties of the obtained board. Example 2 After uniformly kneading 10 kg of the flame-retardant wood powder obtained in Reference Example 1 (pulverized to 200 mesh passes) and 5 kg of polystyrene using a heated roll, the flame-retardant composition was mixed at 50 kg/cm ² and 130 kg. A board was obtained by press molding at ℃ for 3 minutes. Table 1 shows the physical properties of the obtained board. Example 3 10 kg of flame-retardant wood powder obtained in Reference Example 1 (pulverized to 200 mesh passes), polyester resin (manufactured by Showa Kobunshi Co., Ltd., trade name Rigorak, 2% methyl ethyl ketone peroxide and cobalt naphthenate as a polymerization catalyst) After uniformly kneading 20 kg of the premix with a heated roll, this premix was press-molded at 10 kg/cm ² at 70°C for 10 minutes to obtain a board. Table 1 shows the physical properties of the obtained board. Example 4 Flame-retardant pulp chips obtained in Reference Example 2 (fiber length:
A board was obtained in the same manner as in Example 1, except that a material (1.5 to 2.0 mm) was used. Table 1 shows the physical properties of the obtained board. Example 5 Flame-retardant pulp chips obtained in Reference Example 2 (fiber length:
A board was obtained in the same manner as in Example 2, except that a material (1.5 to 2.0 mm) was used. Table 1 shows the physical properties of the obtained board. Example 6 Flame-retardant pulp chips obtained in Reference Example 2 (fiber length:
A board was obtained in the same manner as in Example 3, except that a material (1.5 to 2.0 mm) was used. Table 1 shows the physical properties of the obtained board. Example 7 A board was obtained in the same manner as in Example 1, except that the flame-retardant cotton linter (fiber length: 3 to 7 mm) obtained in Reference Example 3 was used. Table 1 shows the physical properties of the obtained board. Example 8 A board was obtained in the same manner as in Example 2, except that the flame-retardant cotton linter (fiber length: 3 to 7 mm) obtained in Reference Example 3 was used. Table 1 shows the physical properties of the obtained board. Example 9 A board was obtained in the same manner as in Example 3, except that the flame-retardant cotton linter (fiber length: 3 to 7 mm) obtained in Reference Example 3 was used. Table 1 shows the physical properties of the obtained board. Example 10 Flame-retardant rayon fiber obtained in Reference Example 4 (fiber length:
A board was obtained in the same manner as in Example 1, except that 3 to 5 mm) was used. Table 1 shows the physical properties of the obtained board. Example 11 Flame-retardant rayon fiber obtained in Reference Example 4 (fiber length:
A board was obtained in the same manner as in Example 2, except that 3 to 5 mm) was used. Table 1 shows the physical properties of the obtained board. Example 12 Flame-retardant rayon fiber obtained in Reference Example 4 (fiber length:
A board was obtained in the same manner as in Example 3, except that 3 to 5 mm) was used. Table 1 shows the physical properties of the obtained board.

【table】

[Table] As is clear from Table 1, the molded products obtained from the flame-retardant composition of the present invention are significantly lighter in terms of material properties, and resin-based molded products are also superior in terms of flame retardancy. It is a non-combustible material, and the gas generated by combustion does not contain harmful gases such as halogens, and its physical strength has been improved due to the fiber reinforcement effect, making it useful for building materials, fittings, housing equipment components, vehicle components, electrical It is extremely useful as a material or ship material.

Claims (1)

[Scope of Claims] 1. A flame-retardant composition characterized in that it contains a cellulose-based combustible filler made of a resin-based material and a cellulose-based material to which condensed ammonium phosphate is chemically bonded or fixed. 2 Claim 1 in which the cellulosic material is wood flour, pulp fiber, cotton fiber or rayon fiber
Compositions as described in Section. 3 Condensed ammonium phosphate has a degree of condensation of 1 to 60
The composition according to claim 1 or 2, which is a 5 to 40% by weight aqueous solution. 4 The cellulosic flame retardant filler contains 10 parts by weight of condensed ammonium phosphate per 100 parts by weight of the cellulose material.
Claim 1 comprising ~30 parts by weight
The composition according to item 1, 2 or 3. 5 Claims 1 and 2 comprising one or more types of cellulose-based flame retardant filler mixed together.
The composition according to item 3, item 3 or item 4. 6 For 100 parts by weight of flame-retardant pulp, flame-retardant rayon fiber, flame-retardant cotton fiber, or a mixture of two or more thereof, in which a cellulose-based flame-retardant filler is chemically bonded or fixed with condensed ammonium phosphate. Claims 1, 2, 3, 4, or 5 are made by mixing 20 to 60 parts by weight of flame-retardant wood powder made by chemically bonding or fixing condensed ammonium phosphate. Compositions as described in Section. 7. The composition according to claim 1, 2, 3, or 4, wherein the resin-based material is a thermoplastic resin or a thermosetting resin. 8 Claims 1 and 2 are obtained by adding and mixing 50 to 500 parts by weight of cellulose-based flame retardant filler to 100 parts by weight of thermoplastic resin or thermosetting resin.
The composition according to item 1, item 3, item 4 or item 7.