JP3341909B2 - Modified red phosphorus and flame retardant polymer materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified red phosphorus and a flame-retardant polymer material in which red phosphorus coated with electroless plating is coated with titanium oxide and an organic polymer. More specifically, it has a high ignition point, a small amount of phosphine generated, and has a white color tone in which the inherent color of electroless plating-coated red phosphorus is concealed and decolored, and the surface is coated with titanium oxide and an organic polymer. The present invention relates to a modified red phosphorus and a flame-retardant polymer material using the modified red phosphorus.

[0002]

2. Description of the Related Art It is well known that red phosphorus imparts an excellent flame-retardant effect to synthetic resins, and it is actually used as a flame retardant. However, if red phosphorus is used as it is, it reacts with water to cause a hydrolysis reaction accompanied by generation of phosphine gas. Therefore, many modified red phosphorus in which red phosphorus is coated with an organic or inorganic material has been proposed. ing.

For example, a modified red phosphorus obtained by coating red phosphorus with a thermosetting resin (Japanese Patent Application Laid-Open No. 51-105996), a modified red phosphorus obtained by converting the surface of red phosphorus into a metal phosphide and then coating with a thermosetting resin. Phosphorus (JP-A-52-125489) or a modified red phosphorus obtained by coating red phosphorus in a triple layer with aluminum hydroxide, other metal hydroxides, etc. and an inorganic or organic coating agent (JP-A-55-125489). No. 10462), a modified red phosphorus in which the surface of red phosphorus particles is coated with an electroless plating film (Japanese Unexamined Patent Publication No.
3-69704) and the like.

[0004] However, red phosphorus alone or red phosphorus stabilized by the above-mentioned method generally shows an inherent dark dark red color. Therefore, when used as a flame retardant for a resin, the resin becomes an unsuitable color. In order to color the resin material, use of the resin member in which color tone is a problem is restricted.

[0005] The present applicant has already proposed a method for enabling free coloring of a flame-retardant resin by using a modified red phosphorus which obscures the dark dark red inherent in red phosphorus and stabilizes the color. A modified red phosphorus disclosed in JP-A-59-195512 was proposed. This modified red phosphorus is obtained by coating red phosphorus with titanium oxide and an organic polymer, and can achieve a high level of concealment and decoloration of dark red of red phosphorus. There were insufficient points.

[0006]

SUMMARY OF THE INVENTION In order to solve the problems of the prior art, the present invention substantially completely suppresses the generation of phosphine gas accompanying the decomposition of red phosphorus, After exploring ways to conceal and darken the dark dark red color, we conducted extensive research and found that the surface of the red phosphorus particles was coated with an electroless plating film, and then coated with titanium oxide and an organic polymer to achieve the above purpose. The modified red phosphorus which can achieve this was found. Further, they have found that when the modified red phosphorus is blended with a polymer material, a flame-retardant polymer material having excellent flame retardancy can be obtained, and the present invention has been completed.

[0007]

That is, the present invention relates to a modified red phosphorus which is characterized in that red phosphorus coated by electroless plating is coated with titanium oxide and an organic polymer obtained by radical polymerization. .

Further, the present invention relates to a flame-retardant polymer material characterized in that the modified red phosphorus is mixed with 0.5 to 50 parts by weight of P to 100 parts by weight of the polymer material. It is.

Hereinafter, the present invention will be described in detail. The modified red phosphorus of the present invention is obtained by coating electroless plated red phosphorus with titanium oxide and a radically polymerized organic polymer.

First, the details of electroless plating coated red phosphorus (hereinafter referred to as "plated red phosphorus") as a core material of the modified red phosphorus of the present invention are described in JP-A-63-69704. However, the plating red phosphorus refers to stabilized red phosphorus in which the surface of red phosphorus particles is coated with an electroless plating film, and the plating film is not particularly limited as long as it is a metal capable of forming an electroless plating film. However, a metal plating film selected from Fe, Ni, Co, Cu, Zn or Mn or an alloy thereof is particularly practical.
Among them, Ni and its alloys are particularly preferable.

This plated red phosphorus can be produced by a conventionally known electroless plating method. Among these electroless plating methods, a method of producing a plating film on the surface of red phosphorus particles by gradually adding an electroless plating solution to a water-soluble suspension of red phosphorus is preferable.

In the case of using sodium hypophosphite or alkali borohydride as a reducing agent in the electroless plating method, depending on the conditions, some phosphorus or boron inevitably forms a film composition as an alloy. However, it goes without saying that such a film is acceptable in the present invention.

In the case of a film that is easily oxidized, such as a film of Fe or an alloy thereof, the surface of the film may be oxidized with time to form an oxide film. As long as the plating film is formed, any change with time is included in the plating red phosphorus.

The reason for this is that even if there is a slight change in the surface, there is no problem in stabilizing red phosphorus, and rather, when it is necessary to avoid the conductive properties of the metal film, an oxide film is intentionally used. Is required to be formed on the metal plating film, which is sometimes preferable.

The coating amount of the plating film varies depending on the use of the plating red phosphorus, the type of metal, and the like, but in many cases, it is 1 to 50% by weight, preferably 2 to 40% by weight of the total weight of the metal. It is desirable to be within the range. The reason is that if the amount is less than 1% by weight, the suppression of phosphine gas is incomplete, and if it exceeds 50% by weight, it is inappropriate from a practical viewpoint.

The plated red phosphorus in the present invention can be easily distinguished from the original red phosphorus by microscopic observation because the luster unique to the metal is uniformly formed on the particle surface.

The plated red phosphorus in the present invention is stabilized red phosphorus in which the generation of phosphine gas is almost completely suppressed, and the details of the reason are unknown. Therefore, it is considered that the coating of the plating film is formed more strongly than the electroless plating of other base materials.

Next, the modified red phosphorus of the present invention is obtained by coating plated red phosphorus with titanium oxide and an organic polymer obtained by radical polymerization. The coating method is as follows. The reaction can be carried out by adding titanium oxide, a monomer capable of radical polymerization and a polymerization initiator, causing a polymerization reaction at pH 2 to 6, followed by filtration and drying.

In the present invention, the particle diameter of red phosphorus is preferably 100 μm or less in consideration of practical use, and the average particle diameter is preferably 5 to 30 μm, more preferably 10 to 20 μm. Since fine powder is apt to be unstable, about 1
Those having a particle size of μm or less are preferably cut as much as possible.

The concentration of the aqueous suspension of the plated red phosphorus is 5 to 20 parts by weight per 100 parts by weight of water.
A suspension of parts by weight is preferred. That is, in this concentration range, the dispersibility of the suspension becomes good, and it becomes possible to uniformly coat the surface of the particles of the plated red phosphorus with titanium oxide and the organic polymer. When the concentration of the plated red phosphorus is less than 5 parts by weight, the yield of the target product is poor and the economic efficiency is poor. When the concentration exceeds 20 parts by weight, the formed organic polymer serves as a binder, and the aggregation between the plated red phosphorus particles is not preferable. .

Next, the titanium oxide used in the present invention has a pH of
Titanium oxide treated with a positive charge in the aqueous suspensions of Nos. 2 to 6 is preferred, and specific examples thereof include titanium oxide treated with aluminum hydrated oxide or silicon and zinc hydrated oxide. And the like. The particle diameter of titanium oxide is preferably in the range of 0.01 to 1 μm. Further, the crystal system of titanium oxide is preferably a rutile type in view of the degree of concealment.

The amount of titanium oxide added is not particularly limited as long as the required degree of concealment can be obtained, but is usually 30 to 150 parts by weight, particularly 50 to 100 parts by weight, per 100 parts by weight of the plated red phosphorus. The range of parts is preferred.

The monomer which can be used for obtaining the organic polymer in the present invention may be any monomer capable of performing radical polymerization, and specifically, for example, methacrylates such as methyl methacrylate and ethyl methacrylate. And acrylates such as methyl acrylate and ethyl acrylate, methacrylic acid, acrylic acid, styrene, vinyl acetate, acrylonitrile, and the like. These monomers homopolymerize, or copolymerize two or more monomers to form an organic polymer.

The appropriate amount of the monomer to be added to the plating red phosphorus is in the range of 5 to 100 parts by weight, preferably 20 to 80 parts by weight based on 100 parts by weight of the plating red phosphorus.
If the addition amount is less than 5 parts by weight, the titanium oxide that has been electrically coagulated and settles on the surface of the plated red phosphorus particles, and a sufficient covering effect cannot be obtained from the viewpoint of stabilizing the plated red phosphorus, and 100 parts by weight. When used in a large amount beyond the part, a large amount of free polymer that does not coagulate and deposit on the surface of the plated red phosphorus particles occurs considerably due to polymerization that does not substantially contribute to or inhibits coating, or The resulting polymer may act as a binder to remarkably agglutinate the plating red phosphorus to make the particle size coarse, which is not preferable. In addition, such a mixture of the free organic polymer unnecessarily contaminates the polymer material when kneading the obtained modified red phosphorus with the polymer material, and disperses the polymer material in the polymer material. It will also hurt.

When the resulting modified red phosphorus is used as a flame retardant for unsaturated polyester, if the coating is required to have chemical resistance to styrene and the like, a crosslinking agent is copolymerized. By doing so, a coating of an organic polymer having a crosslinked structure can be formed. As the crosslinking agent to be used, a polyfunctional monomer having two or more polymerizable double bonds in one molecule is preferable. For example, ethylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dimethacrylic acid Tetraethylene glycol, 1,3-butylene dimethacrylate,
And trimethylolpropane trimetacholate.

The appropriate amount of the crosslinking agent to be added to the monomer used for coating is 1 to 100 parts by weight of the monomer.
20 parts by weight. If the amount is less than 1 part by weight, the produced organic polymer is inferior in the effect of chemical resistance, and if it exceeds 20 parts by weight, the yield of the produced organic polymer becomes low.

The polymerization initiator used in the present invention includes, for example, organic or inorganic peroxide initiators such as benzoyl peroxide, potassium persulfate, ammonium persulfate and hydrogen peroxide, azobisisobutyronitrile, 2,2 '
Azo compound-based initiators such as -azobis- (2-amidinopropane) dihydrochloride, and one or more kinds of sulfite-based initiators such as sulfite water, sodium hydrogen sulfite, ammonium sulfite, and sulfur dioxide gas. Use in combination.

In the present invention, a modified red phosphorus in which plated red phosphorus is coated with titanium oxide and an organic polymer is produced using the above-mentioned raw materials. Titanium oxide is sufficiently suspended in water to prepare a suspension having a pH of 2 to 6, and a monomer, a polymerization initiator and, if necessary, a crosslinking agent are added thereto to carry out polymerization.

Here, when the pH of the suspension is adjusted to the range of 2 to 6, the surface of the plated red phosphorus particles becomes negatively charged, while
Since the surfaces of the titanium oxide particles are positively charged, both are electrically attracted and the monomer undergoes a polymerization reaction, so that the plated red phosphorus can be efficiently and firmly coated with the titanium oxide and the organic monomer.

With regard to the order of adding the raw materials, it is advantageous to adjust the pH of the aqueous suspension of the plated red phosphorus and titanium oxide as necessary, and then add the monomers, a polymerization initiator, etc. with stirring to effect the polymerization reaction. It is. However, it is not always necessary to carry out in the above order, for example, a monomer, a polymerization initiator, etc. are added to an aqueous suspension of plating red phosphorus to start polymerization, and titanium oxide is added in the middle of polymerization, and if necessary, p
Adjust the H to complete the polymerization, or add a monomer and a polymerization initiator to the aqueous suspension of titanium oxide to start the polymerization, add red phosphorus plating in the middle of the polymerization, and adjust the pH as necessary. It is also possible to use a method in which the polymerization is adjusted to complete the polymerization.

It is sufficient that the polymerization reaction is carried out preferably under an atmosphere of an inert gas such as nitrogen gas at a temperature of 30 to 90 ° C. for 1 to 7 hours. After the completion of the polymerization reaction, the mixture is sufficiently filtered and washed with water according to a conventional method and dried.

According to the present invention, the plated red phosphorus can be easily, efficiently, uniformly and firmly coated with the titanium oxide and the organic polymer. A white color tone can be obtained and stabilized. Plating red phosphorus, or each of the titanium oxides does not agglomerate alone, for example, the state where the plating red phosphorus is uniformly coated with the titanium oxide and the polymer is also observed in electron micrographs, and as is clear in the test examples described later. High whiteness allows more free coloring of polymer materials. Also. High ignition point, low phosphine generation,
A modified red phosphorus coated with an excellent titanium oxide and an organic polymer as a flame retardant is obtained.

Next, the flame-retardant polymer material of the present invention is obtained by blending the above-mentioned modified red phosphorus with a polymer material. The polymer material applicable in the present invention is not particularly limited as long as it is a polymer material, and examples thereof include synthetic resins, rubbers, and wood.

The synthetic resin is a flammable synthetic resin which is required to be flame-retardant when used, and may be either a thermosetting resin or a thermoplastic resin. The mode of use of the synthetic resin can be used, for example, as various molding materials, paints, adhesives, and the like, and the mode is not particularly limited.

Examples of the thermosetting resin include a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, an epoxy resin, a silicon resin, a diacryl phthalate resin and a polyurethane resin.

Examples of the thermoplastic resin include poly-α-olefins such as polyethylene and polypropylene;
Copolymer with other monomer containing at least α-olefin, polystyrene, methacrylic resin, styrene-acrylonitrile copolymer (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), polyvinyl chloride, fluorine resin , Polyamide, polyimide, polycarbonate, polyacetal, thermoplastic polyester, cellulose acetate (cellulose resin), polysulfone thermoplastic polyimide, polyphenylene oxide, polybutylene ionomer resin, and the like.

The rubbers are flammable rubbers which are required to be flame-retardant when used, and include synthetic rubbers. The modes of use include, for example, various molding materials, paints and adhesives. And the like, and the mode is not particularly limited. Examples of the synthetic rubber include SBR, BR, IR, EPM, EPDM, N
BR, CR, IIR, urethane rubber, silicone rubber,
Fluorinated rubbers, thermoplastic elastomers and the like can be mentioned.

As wood, there is mentioned application to flame retardant plywood, but the modified red phosphorus is mainly used in an adhesive. That is, by using an adhesive containing modified red phosphorus in the production of laminated plywood, a fire-resistant and flame-retardant plywood can be obtained. In addition, by blending in a paint for wood use, a flame-retardant coating film can be provided on wood.

In particular, when the modified red phosphorus is blended into various flame-retardant polymer materials in the present invention, the blended amount of the modified red phosphorus is determined based on the amount of the polymer material such as various synthetic resins, rubbers, and wood.
With respect to 0 parts by weight, P is in the range of 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight. Further, a metal hydroxide such as Al, Mg, or Zr can be added to the flame-retardant polymer material. The amount of the metal hydroxide is preferably 0 to 100 parts by weight, based on 100 parts by weight of the polymer material. Is 10-50
It is in the range of parts by weight.

Further, in the present invention, the flame-retardant polymer material may contain other additives which can be usually blended according to the purpose of use, such as plasticity, lubricant, stabilizer, filler, and the like.
A coloring agent, an antioxidant, an ultraviolet inhibitor or the like can be appropriately compounded.

[0041]

The present invention will be specifically described below with reference to examples, comparative examples and test examples.

Example 1 Preparation of Electroless Nickel- Plated Red Phosphorus Red phosphorus powder 10 having a particle diameter of 44 μm or less and an average particle diameter of 24 μm.
0 g was poured into 1 liter of a 0.1 g / l palladium chloride diluted hydrochloric acid solution, stirred for about 5 minutes, filtered, and further repulped and catalyzed. Next, the red phosphorus was put into 1 liter of an aqueous tartaric acid (20 g / l) solution, sufficiently dispersed, and the liquid temperature was raised to 80 ° C. to prepare an aqueous suspension.

Further, the electroless plating solution was divided into solution a (nickel sulfate 224 g / l) and solution b (mixture consisting of sodium hypophosphite 226 g / l and sodium hydroxide 128 g / l), and 41 ml of each was separately 5m at the same time
While stirring at an addition rate of 1 / min, the mixture was added to the aqueous suspension to perform a plating treatment. After the addition of the entire amount, stirring was continued while maintaining the temperature at 80 ° C. until the generation of hydrogen stopped.
Next, after repulping washing and filtration, the resultant was subjected to the next coating reaction.

Observation of the obtained powdered red phosphorus plating powder with a microscope revealed that the surface of the red phosphorus particles had a completely uniform and metallic glossy coating.
As a result of measuring a line diffraction image, it was confirmed that all of the precipitates were nickel metal.

Preparation of Modified Red Phosphorus Water was placed in a 200 ml glass reaction vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube.
ml and the above-mentioned 10 g of electroless nickel-plated red phosphorus were charged and stirred to disperse the electroless nickel-plated red phosphorus in water. Then, 8.7 g of rutile-type titanium oxide treated with hydrated Al (manufactured by Ishihara Sangyo Co., Ltd., trade name: Typek R-630) was added thereto while stirring, and coagulated and deposited on electroless nickel-plated red phosphorus. . The pH of the suspension at this time was 4. Further, while stirring, a monomer liquid obtained by dissolving 0.3 g of triethylene glycol dimethacrylate as a cross-linking agent in 10.0 g of methyl methacrylate is added to sufficiently contact the electroless nickel-plated red phosphorus-titanium oxide aggregated particles. Done.

Thereafter, the temperature of the suspension was raised to 60 to 65 ° C.
Then, 0.07 g (7 ml as a 1% by weight aqueous solution) of 2,2 'azobis (2-amidinopropane) dihydrochloride was added as a polymerization initiator, and the polymerization reaction was performed in a nitrogen atmosphere for 2 hours. After completion of the reaction, the reaction mixture was cooled, the suspension was filtered by suction, washed with water, and the filter cake was dried at 60 to 70 ° C. under reduced pressure until the weight became constant. 24 g of pure red phosphorus were obtained.

Example 2 Using the same apparatus as in Example 1, in the same manner as in Example 1, 100 ml of water, 20 g of electroless nickel-plated red phosphorus,
Rutile-type titanium oxide whose main component is Al-containing hydrated oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: Typek R-8)
20) 14.0 g were added. The pH at this time was 4. Next, 8 g of vinyl acetate and 0.32 g of potassium persulfate as a polymerization initiator (32 m 2 as a 1% by weight aqueous solution)
After l) was added in sequence, polymerization was carried out to obtain 39 g of modified red phosphorus in which the Ni metal color inherent to electroless nickel-plated red phosphorus was hidden and decolored.

Comparative Example 1 The same operation as in Example 1 was performed using untreated red phosphorus to obtain a modified red phosphorus.

Test Example 1 Next, for each of the modified red phosphorus obtained in Examples 1 and 2 and Comparative Example 1, the amount of phosphine (PH ₃ ) generated, whiteness and ignition point were measured. It is shown in FIG.

[0050]

[Table 1]

[0051] (Note) (1) measurement of phosphine generation amount, containment of the sample 0.5g in Mitsusen vessel in N ₂ gas atmosphere, 250 ° C., 1
After holding for a time, the gas in the container is sampled and a phosphine gas detector tube (Gastec detector tube: detected concentration 0.1
5 ppm, manufactured by Kitazawa Sangyo Co., Ltd.)
₃ ) The concentration was evaluated by a gas detection measurement method. (2) The ignition point was measured at 10 ° C. /
The measurement is performed by heating at a heating rate of min.

(3) The whiteness is measured by a photoelectric whiteness meter (Kett).
(C-1 type, Kett Science Laboratory) by comparing the standard white plate with the sample plate compressed and filled with the sample and measuring the reflectance of light transmitted through a predetermined filter. (4) Comparative Example 2 used Al-coated red phosphorus. Al-coated red phosphorus is obtained by converting red phosphorus having an average particle diameter of 20 μm to Al (OH) _3.
10 wt% surface-coated was used.

Examples 3 to 4 and Comparative Example 3 (1) Preparation of resin composition A mixture having the following composition was mixed with a mold (12.7 mm × 12.7 mm).
× 127 mm) and heated and cured at 100 ° C. for 6 hours to prepare an epoxy resin molded article. During the preparation of the test piece, no odor of phosphine occurred, and it was not detected when measured by the above method. Further, the resin molded products of Examples 3 and 4 were grayish white, and the resin molded product of Comparative Example 3 was dark red.

100 parts by weight of epoxy resin (Epicoat 828; product of Yuka Shell Epoxy Co., Ltd.) 80 parts by weight of anhydrous curing agent (hardener; product of Nippon Ciba Geigy Co., Ltd.) 100 parts by weight of aluminum hydroxide (Heidilite H32- I; Showa Light Metal Co., Ltd. product) 6 parts by weight as modified red phosphorus P

[0055] (2) measurement method and its results 1. Measurement of the amount of phosphine generated in the modified red phosphorus 0.5 g of a sample stored for 48 hours in a thermo-hygrostat at 30 ° C. and a relative humidity of 83% was taken and heated in N ₂ gas (2
(50 ° C, 3 hours). The generated PH ₃ amount was measured by gas chromatography, per sample 1g generating PH ₃
It was converted to the amount (μg). Table 2 shows the results.

[0056] 2. Flame resistance test The resin composition was measured by the flame resistance test A method of JIS K-6911. Table 4 shows the results. The resin composition (blank) containing no modified red phosphorus was “flammable”.

[0057]

[Table 2]

(Note) Sample No. of modified red phosphorus No. 1 is the modified red phosphorus obtained in Example 1; 2 is the modified red phosphorus obtained in Example 2; No. 3 used the modified red phosphorus obtained in Comparative Example 1. The same applies to the following examples and comparative examples.

Comparative Example 4 In the resin composition of Example 3, instead of the modified red phosphorus according to the present invention, a thermosetting resin-coated red phosphorus (commercial product A, which itself generates 20 μg / g of phosphine) and An epoxy resin molded product was prepared in the same manner as in Example 3 except that alumina-coated red phosphorus (commercial product B, the amount of phosphine generated itself was 50 to 80 μg / g), and a flame resistance test of the molded product was performed. went. As a result, all had a phosphine odor, and as a result of the measurement,
μg / g phosphine was detected. The epoxy resin molded product was dark red.

Examples 5 to 8 Resin compositions (shown in Table 3) in which a predetermined amount of a modified red phosphorus sample was blended with 100 parts by weight of unsaturated polyester
1 part by weight of a 55% by weight methyl ethyl ketone peroxide curing catalyst per 0 part by weight and an appropriate amount of cobalt naphthenate were blended and uniformly mixed to form a mold (12.7 mm × 1).
(2.7 mm × 127 mm), and the mixture was heated at 100 ° C. for 2 hours and cured to prepare a polyester resin molded article.

During the preparation of the test piece, no odor of phosphine occurred, and it could not be detected by the measurement using the gas detector tube. The resin molded products of Examples 5 to 8 were grayish white. Further, the obtained test piece was subjected to the above-mentioned Example 3
The flame resistance test was carried out by the measurement method shown in FIG. Table 3 shows the results.

[0062]

[Table 3]

Examples 9 to 15 Various thermoplastic resin compositions having the formulations shown in Table 4 were prepared.
After kneading for 10 minutes with two rolls by heating at 80 to 270 ° C,
A test piece (12.7 mm × 3 mm × 12.7 mm) was prepared, and a test for flame resistance was performed. No odor of phosphine occurred during the preparation of this test piece, and it was not detected by the measurement using the gas detection tube. The resin molded products of Examples 9 to 15 were grayish white. Further, a heat resistance test was performed on the obtained test piece. Table 4 shows the results.

[0064]

[Table 4]

(Note) (1) The amount of the modified red phosphorus is 6 parts by weight as P. (2) Flame resistance * is the value of V-2 in the combustion test according to UL-94.
Pass the above.

Comparative Example 5 The above-mentioned thermosetting resin-coated red phosphorus (commercial product A) and alumina-coated red phosphorus (commercial product B) were used in place of the modified red phosphorus in the polyester resin compositions of Examples 5 to 8. A polyester resin molded article was prepared in the same manner as in Examples 5 to 8 except for that, and a flame resistance test of the resin molded article was performed. As a result, all had a phosphine smell, and as a result of the measurement, 50 to 80 μg / g of phosphine was detected. The resin molded product was dark red.

[0067]

As described above, the modified red phosphorus of the present invention is obtained by coating the plated red phosphorus with titanium oxide and an organic polymer obtained by radical polymerization. Phosphorus metallic luster or dark gray color tone is hidden and decolorized, has a white gray white color tone, has a remarkable difference in appearance from conventional red phosphorus flame retardants, and has a high ignition point, The phosphine gas generation is extremely suppressed and the generation of phosphine gas is extremely suppressed.

The flame-retardant polymer material obtained by blending the modified red phosphorus with the polymer material can be arbitrarily colored because the modified red phosphorus has a white-gray white tone. is there.
In addition, when modified red phosphorus is blended with polymer materials such as synthetic resin, rubber, and wood, the generation of toxic and odorous phosphine gas is substantially completely prevented, and a polymer material having excellent flame retardancy is obtained. be able to.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-69704 (JP, A) JP-A-63-95266 (JP, A) JP-A-52-125489 (JP, A) JP-A-62-125 21704 (JP, A) JP-A-59-195512 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01B 25/00 C08K 9/04 CA (STN)

Claims (4)

(57) [Claims] 1. A modified red phosphorus comprising an electroless plating-coated red phosphorus coated with titanium oxide and a radically polymerized organic polymer. 2. A method according to claim 1, wherein 30 to 150 parts by weight of titanium oxide and 5 to 100 parts by weight of radical polymerized organic polymer are coated with red phosphorus based on 100 parts by weight of electroless plating red phosphorus. Modified red phosphorus. 3. The modified red phosphorus according to claim 1, wherein the electroless plating coated red phosphorus is an electroless nickel-coated red phosphorus having a coating amount of 1 to 50% by weight as Ni based on the total weight. 4. A flame-retardant polymer material comprising 100 parts by weight of the polymer material and 0.5 to 50 parts by weight of the modified red phosphorus according to claim 1 as P.