JP2000160164A - Powdery flame-retardant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a powdery flame-retardant capable of being readily powdered in a short time and producing a readily handleable molding product having excellent flame retardance and mechanical strength by making the flame- retardant include a phosphazene compound liquid at a normal temperature, etc., an inorganic fibrous substance and a solid binder in a specific ratio. SOLUTION: This flame-retardant comprises (A) 0.5-80 wt.% of a phosphazene compound such as hexachlorocyclotriphosphazene liquid or viscous solid at a normal temperature, (B) 60.0-19.9 wt.% of an inorganic fibrous substance such as fibrous alkali metal titanate, a fibrous transition metal borate, fibrous titanium oxide, carbon fiber, alumina fiber, glass, fiber, etc., and (C) 35.0-0.1 wt.% of a solid binder such as aluminum hydroxide, magnesium hydroxide, antimony hydroxide, melamine (cyanurate) or thermotropic liquid crystal polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel powdery flame retardant.

[0002]

2. Description of the Related Art Phosphazene compounds used as flame retardants for synthetic resins are generally in liquid form or essentially solid, but may be formed by the production of homologues or analogs during the production process. , A liquid or a viscous solid. This tendency does not change even when the purity of the phosphazene compound is as high as 98% or more.

When adding a flame retardant to a synthetic resin or the like, it goes without saying that a powdery substance is easier to handle and a supply means is simpler than a liquid or viscous solid substance. is there. In the case of packaging and transportation, the powdery substance is more advantageous.

[0004] Generally, in order to powder a liquid or viscous solid substance, a purification treatment method such as a recrystallization method or a fractional distillation method using an organic solvent is carried out. However, such a method not only requires special equipment and energy as a heat source, but also has a drawback that the organic solvent must be recovered and reused.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel powdery flame retardant obtained by pulverizing a liquid or viscous solid phosphazene compound at room temperature by a simple method without the above-mentioned conventional disadvantages. Is to do.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a liquid or viscous solid phosphazene compound, an inorganic fibrous substance and a solid binder are mixed at room temperature. As a result, it has been found that a powdery flame retardant can be obtained without impairing the performance of the phosphazene compound as a flame retardant by an extremely simple method of adhering or adsorbing them, and based on this, the present invention has been completed. .

That is, the present invention comprises mixing a phosphazene compound which is liquid or viscous solid at room temperature, an inorganic fibrous substance and a solid binder.
0.0% by weight, 60.0 to 19.9% by weight of the fibrous substance
And 35.0 to 0.1% by weight of a solid binder.

[0008] Powdering using an inorganic fibrous substance and a solid binder is performed by using a flame retardant which is a liquid or viscous solid at room temperature.
Produces effective results when applied to certain, phosphazene compounds. For example, even if a phosphoric acid ester compound which is used as the same flame retardant as the phosphazene compound and is a liquid or viscous solid at room temperature is powdered with an inorganic fibrous substance and a solid binder, it is possible to obtain a good powdery one. Can not.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The powdery flame retardant of the present invention comprises a liquid or viscous solid phosphazene compound, an inorganic fibrous substance and a solid binder at room temperature as active ingredients.

As the phosphazene compound which is a liquid or viscous solid at room temperature, which is a raw material of the powdery flame retardant of the present invention, any known phosphazene compound can be used. Here, “liquid at normal temperature” means that the viscosity at 25 ° C. is 0.3 mPa · s to 10 Pa
・ It is equivalent to about s, and “viscous solid at room temperature” is 25 ° C
Corresponds to about 10 Pa · s or more.

As the phosphazene compound as the raw material flame retardant, any of the known compounds described in patent publications and literatures can be used. Specifically, for example, James E. Mark, H
arryR. Allcock, Robert West, "Inorganic Polymers"
(Prentice-Hall International, Inc., 1992)
And phosphazene compounds described on page 40.

More specifically, for example, the following (1) to
The compound of (4) can be mentioned. (1) General formula

[0013]

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Wherein m represents an integer of 3 to 25. Two R ^{1 s} are the same or different and represent a phenyl group or an unsubstituted phenyl group substituted by at least one selected from an alkyl group having 1 to 6 carbon atoms and an allyl group. ] The cyclic phosphazene compound represented by these. (2) General formula

[0015]

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[Wherein, n represents an integer of 3 to 1,000.
R ¹ is the same as above. X represents a group -N = P (OR ¹ ) ₃ or a group-
N = P (O) shows the OR ^1. Y represents a group -P (OR ¹ ) ₄ or a group -P (O) (OR ¹ ) ₂ . ] The linear phosphazene compound represented by these. (3) at least one selected from the phosphazene compounds of the above (1) and (2) is selected from the group consisting of an o-phenylene group, an m-phenylene group, a p-phenylene group, a biphenylene group and a general formula

[0017]

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Wherein A is a group —SO_Two-, Group -S-, group
—O— or a group —C (CH_Three)_TwoIndicates-. A group represented by
Crosslinked with at least one type of crosslinking group selected from
Sphazen compounds. The cross-linking group is formed by the above (1) and (2)
R of the phosphazene compound of¹Oxygen sources desorbed
Intervene between children. The group R in this crosslinked phosphazene compound
¹The content of the above, in the phosphazene compound before cross-linking
R¹50 to 99.9% based on the total number of (4) General formula

[0019]

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Wherein R ² represents a cyano-substituted phenyl group. R ³ is an alkyl group having 1 to 18 carbon atoms or 6 carbon atoms.
To 10 aryl groups having 1 to 10 carbon atoms.
At least one group selected from 10 alkyl groups, allyl groups and aryl groups may be substituted. When the R ³ there are two or more, their R ³ together may be the same or may be different. p and q are p>
0, q ≧ 0, indicating a real number satisfying p + q = 2. r
Represents an integer of 3 to 25. A cyclic phosphazene compound represented by the general formula:

[0021]

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Wherein R ² , R ³ , p and q are as defined above. s shows the integer of 3-1000. X ′ is a group —P (O
R ² ) ₄ , group —P (OR ² ) ₃ (OR ³ ), group —P (OR ² ) ₂ (O
R ³ ) ₂ , group —P (OR ² ) (OR ³ ) ₃ , group —P (OR ³ ) ₄ , group
P (O) (OR ² ) ₂ , group -P (O) (OR ² ) (OR ³ ) or group -P
(O) (OR ³ ) ₂ , Y ′ represents a group —N ＝ P (OR ² ) ₃ ,
N = P (OR ² ) ₂ (OR ³ ), group -N = P (OR ² ) (OR ³ ) ₂ ,
Group -N = P (OR ³ ) ₃ , group -N = P (O) OR ² or group -N
= P (O) OR ³ . At least one phosphazene compound selected from the group consisting of linear phosphazene compounds represented by the formula:

As the phosphazene compound, one type can be used alone, or two or more types can be used in combination. It may be a mixture of a cyclic phosphazene compound and a linear phosphazene compound.

Specific examples of the cyclic phosphazene compound (1) and the linear phosphazene compound (2) are as follows.
For example, ammonium chloride and phosphorus pentachloride are
A phosphazene compound obtained by substituting a cyclic and linear chlorophosphazene mixture such as hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene obtained by reacting at about 0 ° C. with a phenoxy group and / or an alkoxy group; A single substance such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene or the like is taken out, and hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene or decafene, in which a phenoxy group and / or an alkoxy group is substituted. Phenoxycyclopentaphosphazene, hexaalkoxycyclotriphosphazene, octaalkoxycyclotetraphosphazene, decaalkoxycyclopentaphosphazene, etc. It can be exemplified Jo phosphazene compound. Further, a linear phosphazene compound in which dichlorophosphazene obtained by heating (220 to 250 ° C.) ring-opening polymerization of hexachlorocyclotriphosphazene is substituted with a phenoxy group and / or an alkoxy group can be exemplified.

Specific examples of the crosslinked phosphazene compound (3) include, for example, phenoxyphosphazene having a crosslinked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), 2,2- (4,4'- Diphenylene) phenoxyphosphazene having a crosslinked structure by an isopropylidene group, phenoxyphosphazene having a crosslinked structure by a 4,4′-oxydiphenylene group, 4,
Phenoxyphosphazene having a crosslinked structure by a 4′-thiodiphenylene group, phenoxyphosphazene having a crosslinked structure by a 4,4′-diphenylene group, and the like can be given.

Specific examples of the phosphazene compound (4) include, for example, monocyanophenoxypentaphenoxycyclotriphosphazene, dicyanophenoxytetraphenoxycyclotriphosphazene, tricyanophenoxytriphenoxycyclotriphosphazene, and tetracyanophenoxydiphenoxycyclotriphosphazene. Phosphazenes, cyclotriphosphazene compounds such as pentacyanophenoxymonophenoxycyclotriphosphazene, monocyanophenoxyheptaphenoxycyclotetraphosphazene, dicyanofenoxyhexaphenoxycyclotetraphosphazene, tricyanophenoxypentaphenoxycyclotetraphosphazene, tetracyanophenoxytetraphenoxycyclo Tetraphosphazene, pentacyanophenoxide Phenoxycyclotetraphosphazene, hexacyanophenoxydiphenoxycyclotetraphosphazene, cyclotetraphosphazene compounds such as heptacyanophenoxymonophenoxycyclotetraphosphazene, cyclic phosphazene compounds such as cyclopentaphosphazene compounds in which a cyanophenoxy group and a phenoxy group are mixed and substituted, Examples include a linear phosphazene compound in which a cyanophenoxy group and a phenoxy group are mixed and substituted.

Among these, in the cyclic phosphazene compound (1), m is an integer of 3 to 8, in the linear phosphazene compound (2), n is an integer of 3 to 25, and (3) In the crosslinked phosphazene compound of
Preferred are those in which A is a group —SO ₂ —, group —S— or —C (CH ₃ ) ₂ —, and the phosphazene compound (4) in which a cyanophenoxy group and a phenoxy group are mixed and substituted.

The purity of the phosphazene compound depends on its raw material,
Depends on manufacturing method and manufacturing conditions, but usually 98-99%
It is about. The purity of the phosphazene compound that can be used in the present invention is not particularly limited, but is usually 90% or more, and preferably 95% or more. When the purity is in this range, powdering can be performed easily and in a short time, and a powder having a more favorable powder state can be obtained.

Examples of the inorganic fibrous substance which is a raw material of the powdery flame retardant of the present invention include fibrous alkali metal titanate, fibrous transition metal borate, fibrous alkaline earth metal borate, and fiber. Zinc oxide, fibrous titanium oxide, fibrous magnesium oxide, fibrous gypsum, fibrous aluminum silicate (mineral name mullite), fibrous calcium silicate (mineral name wollastonite), fibrous silicon carbide, fibrous titanium carbide, Fibrous silicon nitride, fibrous titanium nitride, carbon fiber, alumina fiber, alumina-silica fiber, zirconia fiber,
Quartz fiber and the like can be mentioned. Representative fibers of fibrous alkali metal titanate, fibrous transition metal borate and fibrous alkaline earth metal borate include potassium titanate fiber, aluminum borate fiber, and magnesium borate fiber. . Among these, fibrous alkali metal titanate, wollastonite,
Magnesium borate fiber and the like, and particularly preferred are fibrous alkali metal titanate, wollastonite and the like. These may be used alone or in combination of two or more.

The above-mentioned inorganic fibrous substance is produced based on methods described in publicly known patent publications and literatures. For example, fibrous zinc oxide is disclosed in JP-B-60-5.
No. 529, JP-B-3-51657, etc., fibrous magnesium oxide is disclosed in JP-A-60-11223 and JP-A-61-210000, and fibrous gypsum is disclosed in JP-B-58-12235. , Tokiko Sho 58
For example, Japanese Patent Publication No. 4-79656 discloses fibrous aluminum silicate (mineral name: mullite).
Japanese Patent Publication No. Hei 7-96480 discloses fibrous calcium silicate (mineral name wollastonite).
No. 199, Japanese Patent Application Laid-Open No. 9-40840, etc.
For example, Japanese Patent Publication No. 59-45638 and Japanese Patent Application Laid-Open No.
For example, Japanese Patent Application Laid-Open No.
JP-A-2-17119 and JP-A-57-17500 disclose fibrous titanium nitride.
8 and JP-A-7-173000.

As the potassium titanate fiber and wollastonite, those having an aspect ratio of 10 or more can be preferably used. The aspect ratio means fiber length / fiber diameter. If it is significantly lower than 10, a sufficient flame retardant effect cannot be obtained. Usually the average fiber diameter is 0.05 to 2.0 μm
And an average fiber length of about 1 to 500 μm can be suitably used.

Of the above potassium titanate fibers and wollastonite, those having a pH of 6.0 to 9.5 are particularly preferably used. Here, the pH of the potassium titanate fiber and wollastonite is defined as a value obtained by stirring a 1.0% by weight aqueous slurry of potassium titanate fiber or wollastonite (using deionized water) for 10 minutes and then further stirring. It refers to a value obtained by measuring the pH of the aqueous slurry at 20 ° C. pH
When it exceeds 9.5, when the powdery flame retardant made from this is mixed with the resin to be flame retarded, the physical properties and heat discoloration resistance of the resin may deteriorate, which is not preferable.
On the other hand, when the pH is extremely lower than 6.0, not only does the effect of improving the strength of the molded article of the resin composition obtained by blending the powdered flame retardant made from the raw material with the resin to be flame retarded, but also the residual acid This may cause corrosion of a processing machine, a mold, and the like, which is not preferable.

The solid binder in the present invention has a role of linking the phosphazene compound with the inorganic fibrous substance. In particular, the feature is that the phosphazene compound, the inorganic fibrous substance, and the solid binder specifically interact with each other. Further, the solid binder also has no function of binding the resin to be flame retarded and the powdered flame retardant of the present invention,
As a result, it contributes to the improvement of the flame retardancy and mechanical properties of the resin after kneading and molding.

Examples of the solid binder as a raw material of the powdery flame retardant of the present invention include aluminum hydroxide, magnesium hydroxide, antimony oxide, magnesium sulfate, calcium sulfate, barium sulfate, aluminum sulfate, boric acid, magnesium carbonate, and calcium carbonate. Inorganic salts such as ammonium ammonium sulfate, potassium aluminum sulfate, sodium aluminum sulfate and ammonium phosphate;
Organic compounds such as sodium toluenesulfonate, sodium 1-naphthalenesulfonate, sodium 2-naphthalenesulfonate, guanidine, guanidine carbonate, melamine cyanurate, melamine, and thermotropic liquid crystal polymer can be given. One of these solid binders can be used alone, or two or more can be used in combination.

Among these solid binders, magnesium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, sodium 1-naphthalenesulfonate, melamine cyanurate, thermotropic liquid crystal polymer and the like are preferable.
Particularly preferred are magnesium sulfate, barium sulfate, aluminum hydroxide, aluminum sulfate and the like. Preferred among the thermotropic liquid crystal polymers are those having p-hydroxybenzoic acid and polyethylene terephthalate as main constituent units, those having p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as main constituent units, and the like. Can be mentioned.

With respect to the inorganic salts as the solid binder, the average water content is 5.0% by weight or less, the pH is 3 to 9, the average particle size is 0.1 to 100 μm, and the specific surface area is 1 to 500 m ² /
g, preferably having an average moisture content of 1.0% by weight or less, pH
4 to 8, average particle diameter of 1 to 50 μm and specific surface area of 10 to 5
More preferably, it is 00 m ² / g. The inorganic salts are usually in a powder form.

The organic compound as the solid binder has an average water content of 2.0% by weight or less and a pH of 3 to
9, average particle size 0.5 to 1000 μm and specific surface area 1 to 1
Is preferably a 500m ² / g, the average water content 0.5 wt% or less, pH 4-8, an average particle size 1~500μm and specific surface area 10 to 500 m ² / g is more preferable. The organic compound is preferably in a powder form at the time of use.

As the above-mentioned solid binder, those which are generally commercially available can be used. Further, it may be manufactured based on methods described in publicly known patent publications and literatures. For example, a method for producing a thermotropic liquid crystal polymer is described in Engineering Plastics Utilization Guide (Nikkan Kogyo Shimbun), pp. 178-187, and Industrial Materials (Nikkan Kogyo Shimbun, Vol. 37, No. 9, 1989), No. 18.
75 pages, and JP-A-9-59524.

As the powdery flame retardant of the present invention, in addition to the inorganic fibrous substance and the solid binder, conventionally known crosslinking agents and fillers may be used in combination.

Examples of the crosslinking agent include divinylbenzene, 1,5-hexadiene-3-yne, hexatriene, divinyl ether, divinylsulfone, diallyl phthalate, 2,6-diacryloylphenol, diallyl carbinol, and dialdehyde Examples of the compound include a compound, a dicarboxylic acid compound, a diamine compound, a diisocyanate compound, a bisepoxy compound, and a bisethyleneimine compound.

Examples of the filler include talc, calcium carbonate, starch, clay, wood powder, asbestos, mica, pulp powder and the like.

The powdery flame retardant of the present invention is prepared by mixing a liquid or viscous solid phosphazene compound at room temperature with an inorganic fibrous substance and a solid binder to adhere or adsorb the phosphazene compound to the fibrous substance. The phosphazene compound is usually a liquid or viscous solid at room temperature.
It contains 0.0% by weight, 60.0 to 19.9% by weight of an inorganic fibrous substance and 35.0 to 0.1% by weight of a solid binder. Preferably, 35.0 to 50.0% by weight of a phosphazene compound which exhibits a liquid or viscous solid state at room temperature, 40.0 to 35.0% by weight of an inorganic fibrous substance, and 30.0 to 10.0% of a solid binder % By weight.

When the content of the phosphazene compound is 80.0
If the amount exceeds 10% by weight, the adhesiveness remains, and a powdery flame retardant in an appropriate state cannot be obtained, which is disadvantageous in terms of cost. If the amount is less than 0.5% by weight, the flame retardancy deteriorates. When the content of the inorganic fibrous substance exceeds 60.0% by weight, the relative concentration of the flame retardant is diluted, and the flame retardant performance is reduced. When the content is less than 19.9% by weight, the whole has a sticky feeling and powder particles. The diameter becomes uneven. If the content of the solid binder exceeds 35.0% by weight, mechanical properties and the like of the resin after molding are reduced. If the content is less than 0.1% by weight, powdering is difficult to achieve.

The powdery flame retardant of the present invention is obtained by mixing a liquid or viscous solid phosphazene compound at room temperature with an inorganic fibrous substance and a solid binder, and adhering the phosphazene compound to the surface of the inorganic fibrous substance. It can be prepared by adsorption. A known method can be used for the mixing, and examples thereof include a method using a mixer with a stirrer such as a plow plate mixer, a ribbon mixer, and a screw mixer. As a specific method of powdering, a required amount of an inorganic fibrous substance and a solid binder are charged in advance to a mixer equipped with a stirrer, and the inorganic fibrous substance and the solid binder are stirred and mixed at room temperature under a liquid or viscous state. The phosphazene compound, which is in the form of a dense solid, is added little by little, for example, dropwise, and the whole is powdered. The stirring rotation speed of the mixer varies depending on the model, form, etc., but is generally 100 to
About 5,000 rpm is appropriate, and 500 to 1,000
0 rpm is more preferred. In this pulverization, when the phosphazene compound to be added is a liquid substance having a relatively low viscosity, the phosphazene compound can be directly supplied to the above mixer using a known liquid injection device. Further, when the phosphazene compound to be added has a high viscosity or is a viscous solid such as a wax, after heating with a heater such as an oven in advance, the viscosity is adjusted to 0.01 to 1 Pa · s at 25 ° C. , Preferably in a state of being reduced to 0.05 to 0.5 Pa · s. After finishing the addition of the phosphazene compound,
Further, stirring and mixing are continued for 0.5 to 10 minutes, preferably 1 to 2 minutes to complete the pulverization of the compound.

Thus, the powdered flame retardant of the present invention is obtained. The powdery flame retardant of the present invention can be suitably used for flame retarding various synthetic resins. When the flame retardant of the present invention is kneaded with a resin, to obtain a more uniform dispersibility of the flame retardant,
It is preferable that the particles have a mean particle diameter of about 500 μm to 4 mm, preferably 1 to 3 mm, through a sieve of 16 to 16 mesh, preferably 6 to 10 mesh. In addition, "kneading" means that when a powdered flame retardant is mixed with a resin, a shearing force is simultaneously applied to the resin and the powdered flame retardant to uniformly disperse the powdered flame retardant inside the resin.

Examples of the resin to which the powdered flame retardant of the present invention can be applied include polyethylene, polypropylene, polyisoprene, polybutadiene, polystyrene, impact-resistant polystyrene (HIPS), acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene. Styrene resin (ABS resin), methyl methacrylate butadiene styrene resin (MBS resin), methyl methacrylate acrylonitrile butadiene styrene resin (MABS resin), acrylonitrile acrylic rubber styrene resin (AAS resin), polyalkyl (meth) Acrylate, aromatic polycarbonate (PC), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether sulfone (PES), polysulfone (PSU) , Polybutylene terephthalate (P
BT), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (P
A), polyetherketone (PEK), polyetheretherketone (PEEK), polyamideimide (PA
I), polyetherimide (PEI), polyimide (P
Examples thereof include thermoplastic resins such as I) and thermosetting resins such as epoxy resins. These can be used alone or in combination of two or more.

In the case where the powdered flame retardant of the present invention is kneaded with a synthetic resin to obtain a flame retardant resin composition, usually, 20 to 60 parts by weight of the powdered flame retardant per 100 parts by weight of the resin. It is preferable to add about 25 to 50 parts by weight. When the amount of the powdered flame retardant exceeds 60 parts by weight, the mechanical properties of the flame-retardant resin composition are deteriorated, and the cost is disadvantageous. On the other hand, when the amount is less than 20 parts by weight, the flame retardancy becomes insufficient. Are not preferred.

When the powdered flame retardant of the present invention is kneaded with various synthetic resins to obtain a flame-retardant resin composition, a kind and amount of a resin additive which does not inhibit the properties of the flame retardant are appropriately added. It can be added in combination. Known additives can be used as the resin additive, for example, other flame retardants, ultraviolet absorbers, light stabilizers, antioxidants, light shielding agents, metal deactivators, quenchers, heat stabilizers, lubricants, Examples include release agents, colorants, antistatic agents, antioxidants, plasticizers, impact strength improvers, fillers, compatibilizers, and the like.

The powdered flame retardant of the present invention does not completely contain a halogen element. A flame-retardant molded article obtained by kneading and molding the powdered flame retardant and various resins is a UL-94 flame retardant test method (Test for Flammability of Plastic Mat).
erials for Parts in Devices and Appliances UL-94, F
Ourth Edition) can achieve V-0 level flame retardancy.

The flame-retardant resin composition obtained by mixing the powdered flame retardant of the present invention with a synthetic resin has excellent mechanical properties and flame retardancy after molding. The composition can be formed into various molded articles by, for example, injection molding, sheet extrusion, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding, and the like.

The molding resin composition obtained by the above method can be used for electricity, electronics, communications, agriculture, forestry and fisheries, mining, construction, food,
Textile, clothing, medical, coal, petroleum, rubber, leather, automobile,
It can be used in industrial fields such as precision equipment, wood, furniture, printing and musical instruments. For example, printers, personal computers, word processors,
Office work such as keyboard, PDA (small information terminal), telephone, facsimile, copier, ECR (electronic cash register), calculator, electronic notebook, electronic dictionary, card, holder, stationery, etc.
OA equipment, washing machine, refrigerator, vacuum cleaner, microwave oven, lighting equipment, game machine, iron, kotatsu and other home appliances, TV,
VTR, video camera, boombox, tape recorder,
AV equipment such as minidiscs, CD players, speakers, liquid crystal displays, etc., connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, etc. -Can be used for applications such as electronic components and communication equipment. In addition, seats (filling, dress material, etc.), belts, ceiling covering, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers, airbags, insulating materials, suspenders, suspenders Obi, electric wire covering material, electric insulation material, paint, coating material, overlay material, floor material, corner wall, deck panel, covers, plywood, ceiling plate, partition plate, side wall, carpet, wallpaper, wall material, exterior Automobiles, vehicles, ships, aircraft and construction materials such as materials, interior materials, roofing materials, soundproofing boards, heat insulating boards, window materials, clothing, curtains, sheets, plywood, plywood, carpets, doormats, sheets, buckets It is suitable for use in daily life and sporting goods such as hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments and the like.

[0052]

The present invention will be described more specifically with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, Comparative Examples and Test Examples.
Unless otherwise specified, “parts” and “%”
It means "part by weight" and "% by weight", respectively.

Synthesis Example 1 (Synthesis of phenoxyphosphazene (compound 1)) 1.30 mol (123.0 g) of phenol was placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser.
Was added, and 500 ml of tetrahydrofuran (THF) was added to dissolve uniformly. Next, after charging 7.6 g of metallic sodium at 25 ° C. or lower, the temperature was raised to 61 ° C. over 1 hour,
Stirring was continued at 61 to 68 ° C for 6 hours to prepare a sodium phenolate solution.

In parallel with the above reaction, 0.5 unit mol (58 g) of dichlorophosphazene oligomer (trimer 59%, tetramer 12%, 5 and hexamer 11%, heptamer 3
%, A mixture of octamer and 15%) in a 2-liter four-necked flask is prepared in a 2-liter four-necked flask. The phenolate mixed solution was added dropwise.
After the dropwise addition, the mixture was stirred and reacted at 71 to 73 ° C. for 15 hours.

After completion of the reaction, the reaction mixture was concentrated,
After re-dissolving in 5 ml of chlorobenzene, washing with water, washing with 5% aqueous sodium hydroxide 3 times, washing with 5% sulfuric acid, washing with 5% aqueous sodium bicarbonate and washing with water 3 times are successively performed. 108 g of a product were obtained. Yield 98.5%.

The weight average molecular weight (Mw) of the product by GPC analysis was 810 in terms of polystyrene, and TG / D
The melting temperature (Tm) by TA analysis was 103 ° C., and the 5% weight loss temperature (T ₅ ) and the decomposition onset temperature (Td) were each 33.
0 ° C and 347 ° C. In addition, the residual chlorine amount (Hy-
Cl) was 0.09%, and it was confirmed from the phosphorus and CHN elemental analysis values that the compound had the structural unit of the following chemical structural formula.

Compound 1: [N = P (-O-Ph) _2.00 ] -Ph in the above formula represents a phenyl group. Hereinafter, the same applies.

Synthesis Example 2 (Synthesis of phenoxyphosphazene (compound 2) having a crosslinked structure using 4,4'-sulfonyldiphenylene (bisphenol S residue)) 1.25 mol (118.0 g) of phenol and 0.03
The reaction was carried out in the same manner as in Synthesis Example 1 using 3 mol (8.3 g) of bisphenol S to obtain a pale yellow wax. 91.5% yield.

The weight average molecular weight (Mw) of the product by GPC analysis was 820 in terms of polystyrene, and the 5% weight loss temperature (T ₅ ) and decomposition initiation temperature (Td) were each 342.
° C and 357 ° C. In addition, the residual chlorine amount (Hy-C
l) is ≦ 0.01%, and it was confirmed from the phosphorus and CHN elemental analysis values that the compound had the structural unit of the following chemical structural formula.

Compound 2: [N = P (-O-Ph-SO ₂
-Ph-O-) _0.05 (-O-Ph) _1.90 ] -Ph- in the above formula represents a p-phenylene group.

Comparative Synthesis Example 1 (Synthesis of Resorcinol-bis (diphenylphosphate) (Compound 3)) 2,6-xylenol 1.9 was placed in a 2 L four-necked flask.
2 mol (234.4 g), 19.2 g of xylene, and 0.02 mol (1.4 g) of magnesium chloride were added and mixed by heating. When the temperature of the reaction solution reached 120 ° C., 1.0 mol (147.2 g) of phosphorus oxychloride was added over about 2 hours. The hydrochloric acid gas generated at this time was led to a water scrubber. After the addition of phosphorus oxychloride was completed, the temperature of the reaction solution was gradually raised to 180 ° C over 2 hours to complete the reaction.

Next, 0.53 mol (52.8 g) of resorcinol and 0.01 mol of aluminum chloride (1.
4g), heat and mix, and gradually raise the reaction temperature to 180 ° C.
Until 2 hours. After stirring at the same temperature for 2 hours,
Stirring was further performed for 2 hours under reduced pressure of 200 mmHg to complete the reaction. After the completion of the reaction, 330 g of xylene was added to the reaction solution.
33 g of 10% aqueous hydrochloric acid was added, and the mixture was stirred to remove the remaining catalyst and the like, and further washed with 99 g of 4% saline.

To a mixture of the obtained compound 3 and a solvent (the concentration of the compound 3 was about 50%) was added 1.0 g of 2,6-di-tert-butyl-p-cresol (0.3 g to the compound 3).
%) And 132 g of a 3% aqueous sodium hydroxide solution were added, and the mixture was heated to 70 ° C. and heated and stirred for 1 hour. Next, 132 g of the oil phase of the reaction solution was washed with 6% saline at 70 ° C., and further washed with 132 g of 4% oxalic acid solution at 90 ° C. to obtain 653 g of an oil phase (the concentration of compound 3 was about 50%).
I got Xylene was removed from the obtained oil phase under reduced pressure to obtain Compound 3 as an oil. 99.2% yield.

Chemical structural formula of compound 3: [(2,6-Me ₂ C ₆ H ₃ O) ₂ P (＝ O) OC ₆ H ₄ OP (＝ O) (2,
6-Me ₂ C ₆ H ₃ O) ₂ ] Example 1 A supermixer (trade name “SM-V-20”, content 20 liters, manufactured by Kawada Seisakusho) was mixed with potassium titanate fiber (trade name “Tismo N”). -102 ", Otsuka Chemical Co., Ltd.
1350 g) and anhydrous magnesium sulfate (trade name "Dry magnesium sulfate SN-00", Makai Chemical Industry Co., Ltd.)
810, powder having an average moisture content of 0.8% by weight or less, a pH of 7.8, an average particle size of 45 μm, and a specific surface area of 170 m ² / g.
g of phenoxyphosphazene (compound 1 obtained in Synthesis Example 1) 1 which was previously heated in a 130 ° C. oven for 1 hour while stirring at room temperature at 570 rpm for 1 hour.
350 g were added little by little from the upper inlet over 5 minutes. After the addition, at room temperature for another 2 minutes at 700 rpm
Then, stirring was continued to complete powderization, and 3510 g of the powdery flame retardant of the present invention was produced.

Examples 2-3 In place of potassium titanate fiber, wollastonite (trade name "Vistal", manufactured by Otsuka Chemical Co., Ltd., Example 2) or magnesium borate fiber (trade name "PGM", Otsuka Chemical) A powdered flame retardant of the present invention was produced in the same manner as in Example 1 except that Example 3) manufactured by Co., Ltd. was used.

Example 4 Compound 2 (Synthesis Example 2) was used in place of Compound 1, and aluminum sulfate (trade name "Taiace S100", manufactured by Daimei Chemical Co., Ltd., average moisture content) was used in place of anhydrous magnesium sulfate as a solid binder. 0.9% by weight or less, pH 6.0, powder having an average particle diameter of 8 μm and a specific surface area of 380 m ² / g)
Was used in the same manner as in Example 1 except that each was used to produce a powdered flame retardant of the present invention.

Examples 5 to 8 As a solid binder, aluminum hydroxide (reagent, manufactured by Kanto Chemical Co., Ltd., having an average water content of 0.5% by weight or less, pH 6.5, an average particle diameter of 4 μm and a specific ratio instead of anhydrous magnesium sulfate) was used. Powder having a surface area of 430 m ² / g, Example 5), a thermotropic liquid crystal polymer (trade name “Novaculate E3”)
21 ", Mitsubishi Engineering-Plastics Corporation
Powder having an average water content of 0.3% by weight or less, pH 6.0, an average particle diameter of 500 μm and a specific surface area of 20 m ² / g, Example 6), sodium 1-naphthalenesulfonate (reagent, Katayama Chemical Co., Ltd.) Example 7) or barium sulfate (reagent, manufactured by Kanto Chemical Co., Ltd., average moisture 1.0% by weight or less, p
H7.0, average particle diameter 9 μm, and specific surface area 480 m ² /
Except for using g of the powder, Example 8), the procedure of Example 2 was repeated to produce a powdered flame retardant of the present invention.

Comparative Example 1 A powdered flame retardant was produced in the same manner as in Example 1 except that anhydrous magnesium sulfate was not used.

Comparative Examples 2-3 Compound 3 (Comparative Synthesis Example 1, Comparative Example 2) in place of Compound 1
Or the same operation as in Example 2 except that triphenyl phosphate (reagent, Wako Pure Chemical Industries, Ltd., Comparative Example 3) was used,
A powdered flame retardant was produced.

Comparative Example 4 A powdered flame retardant was produced in the same manner as in Example 2 except that anhydrous magnesium sulfate was not used.

Test Example 1 200 g of each of the powdered flame retardants obtained in Examples 1 to 8 and Comparative Examples 1 to 4 was used according to JIS with a diameter of 203 mm and a height of 45 mm.
It was placed in a 2.0 mm stainless steel sieve, shaken for 1 minute, and the ratio (% by weight) of the powder passing through the sieve was measured. Using this as an index, the powdered state was evaluated according to the following criteria.

The powder was completely pulverized (the powder passing through the sieve was 80
%), △ indicates that the powder was partially unrefined (the powder passed through the sieve was 79 to 50% by weight), and x indicates incomplete powdering (the powder that passed the sieve was 49% by weight). % By weight).

The average particle diameter (m) of each powdered flame retardant
m) with a particle size distribution analyzer (trade name “Luzex II
I ", manufactured by Nicole Corporation).

Table 1 below shows the raw material composition ratio (%), average particle diameter, and powdered state of each powdered flame retardant.

[0075]

[Table 1]

In Table 1, the compounds represented by the abbreviations are as follows.

TISMO: potassium titanate fiber (trade name “Tismo N-102”, manufactured by Otsuka Chemical Co., Ltd.).

WN: Wollastonite (trade name “Vistal” manufactured by Otsuka Chemical Co., Ltd.).

PGM: magnesium borate fiber (trade name "PGM", manufactured by Otsuka Chemical Co., Ltd.).

TPP: triphenyl phosphate (reagent, manufactured by Wako Pure Chemical Industries, Ltd.).

NASA: sodium 1-naphthalenesulfonate (reagent, manufactured by Katayama Chemical Industry Co., Ltd.)

LCP: Thermotropic liquid crystal polymer (trade name “Novaculate E321”, manufactured by Mitsubishi Engineering-Plastics Corporation).

From Table 1, it is clear that the powdered flame retardant of the present invention has a suitably small average particle size and shows a good powdered state.

Test Example 2 The powdered flame retardants of Examples 1 to 8 and Comparative Examples 1 to 4 and the synthetic resin were mixed in a twin screw extruder (trade name “S1-KRC, 25mm Knader ",
Melt kneading at 250 ° C. using Kurimoto Iron Works Co., Ltd.)
Pelletized, No. 1 to 14 flame-retardant resin compositions were produced.

[0085]

[Table 2]

In Table 2, the synthetic resins indicated by the abbreviations are as follows.

PC / ABS: Polycarbonate resin (trade name “Iupilon S-2000”, manufactured by Mitsubishi Engineering Co., Ltd.) / ABS resin (trade name “Santac UT-
61 ", manufactured by Mitsui Chemicals, Inc.) = 3/1 (weight ratio) mixture.

PC / PBT: A mixture of polycarbonate resin (“Iupilon S-2000”) / polybutylene terephthalate resin (trade name “PBT-1200S”, manufactured by Toray Industries, Inc.) = 7/3 (weight ratio).

PPE / HIPS (trade name “Xylon X-
9108 ", manufactured by Asahi Kasei Corporation).

The No. obtained above was obtained. An injection molding machine (trade name “MINIMAT”) using the flame-retardant resin composition of Nos. 1 to 14
-26 / 15B ", manufactured by Sumitomo Heavy Industries, Ltd.), and the physical properties were evaluated by the following methods.

1. Flexural modulus: measured by a method based on JIS-K7203.

[0092] 2. Heat deformation temperature: Measured under a load of 18.6 kgf / cm ² according to ASTM D-648.

3. Izod impact strength (IZ): JIS
It measured at 23 degreeC according to -K7110.

4. Melt flow rate (MFR): JI
The measurement was carried out at 240 ° C. under a load of 10 kgf according to S-K7210.

5. Flame retardancy: UL-94 test method (Test f
or Flammability of Plastic Materials for Parts in
An evaluation test was performed using a test piece having a thickness of 1/16 inch, a length of 5 inches and a width of 0.5 inch based on Devices and Appliances UL-94, Fourth Edition). The evaluation criteria are shown below.

V-0: All of the following A to E are satisfied.

A: Each set of five test pieces was exposed to flame
Flaming (to keep burning with flame) is less than 10 seconds. B: Flaming after 10 times of flame contact, within 50 seconds, C: 5 pieces per set. Flaming of any specimen to clamp
No; D; none of the five test pieces in a set drip Flaming granules that ignite cotton 305 mm below; E; Glow none of the five test pieces in a set after the second flame contact
ing (flames and does not burn, but remains as a glowing fire) within 30 seconds.

V-1: All of the following A to E are satisfied.

A: Each set of five test pieces was exposed to flame
Flaming within 30 seconds, B; Flaming after 10 times of flame contact, 2 times for 5 pieces per set, within 250 seconds, C and D; same as V-0, E; 5 pieces per set All specimens were glowed after the second flame contact.
ing is within 60 seconds.

V-2: All of the following A to E are satisfied.

A, B, C and E; the same as V-1; D; Flaming granules which ignite cotton 305 mm below at least one of five test pieces per set are dropped.

HB: In the horizontal test, none of the three test pieces per set burned up to the 101.6 mm mark after the flame contact.

6. Drip property: During the flame retardancy test, the presence or absence of Flaming particles (drip) that ignite cotton was checked.

Table 3 shows the test results.

[0105]

[Table 3]

From Table 3, it is found that the molded article No. No. was obtained from the resin composition containing the powdered flame retardant of the present invention. Nos. 1 to 9 are molded products obtained from the resin composition containing the powdered flame retardant of Comparative Example. It is clear that it has significantly better flame retardancy and has the same or higher mechanical strength than 10-14.

[0107]

According to the powdery flame retardant of the present invention, by mixing a liquid or viscous solid phosphazene compound at room temperature with an inorganic fibrous substance and a solid binder, it is easy to handle in powder form. Yes, it can be powdered in a short time without being subjected to a special process, and can be obtained by a simple and industrially advantageous method. A particularly remarkable effect is exhibited in that it is excellent in properties and mechanical strength.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinji Nakano 463 Kasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Inside the Tokushima Research Institute (72) Inventor Takashi Kameshima 463, Kasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Inside the Tokushima Research Institute Co., Ltd. (72) Inventor Yoichi Nishioka 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Inside Otsuka Chemical Co., Ltd. F-term (reference) in Tokushima Research Laboratory 4H028 AA38 AB02 BA06 4J002 AA001 AC021 BB001 BC001 BG001 BN001 CF041 CF162 CG001 CH071 CH091 CL001 CL062 CL082 CM041 CN011 CN031 DA017 DE077 DE078 DE097 DE107 DE128 DE137 DE147 DJ0107 DG 147 ER028 EU198 EV258 EW048 EW156 FA047 FD132 FD137 FD138 GC00 GH00 GJ00 GL00 GN00 GQ00

Claims (3)

[Claims] 1. A phosphazene compound which is a liquid or viscous solid at room temperature, an inorganic fibrous substance and a solid binder are mixed, and 0.5 to 80.0% by weight of the phosphazene compound is
A powdery flame retardant containing 60.0 to 19.9% by weight of the fibrous substance and 35.0 to 0.1% by weight of a solid binder. 2. An inorganic fibrous substance comprising: fibrous alkali metal titanate, fibrous transition metal borate, fibrous alkaline earth metal borate, fibrous zinc oxide, fibrous titanium oxide,
Fibrous magnesium oxide, fibrous gypsum, fibrous aluminum silicate, fibrous calcium silicate, fibrous silicon carbide, fibrous titanium carbide, fibrous silicon nitride, fibrous titanium nitride,
The powdery flame retardant according to claim 1, which is at least one selected from carbon fiber, alumina fiber, alumina-silica fiber, zirconia fiber, glass fiber, and quartz fiber. 3. A solid binder comprising aluminum hydroxide,
Magnesium hydroxide, antimony oxide, magnesium sulfate, calcium sulfate, barium sulfate, aluminum sulfate, boric acid, magnesium carbonate, calcium carbonate, aluminum ammonium sulfate, aluminum potassium sulfate, sodium aluminum sulfate, ammonium phosphate,
The powdery flame retardant according to claim 1, which is at least one selected from sodium toluenesulfonate, sodium naphthalenesulfonate, guanidine, guanidine carbonate, melamine cyanurate, melamine, and a thermotropic liquid crystal polymer.