JP2000109705A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition having excellent flame- retardancy, generating little toxicity in combustion and developing excellent moldability and moisture-resistance by compounding a thermoplastic resin with a flame-retardant composed of an aromatic organic phosphonic acid amine salt in combination with a water-containing phyllosilicate. SOLUTION: The objective composition contains (A) 100 pts.wt. of a thermoplastic resin (preferably polypropylene resin), (B) 20-150 pts.wt. of an aromatic organic phosphonic acid amine salt and (C) 0.1-50 pts.wt. of a phyllosilicate (preferably vermiculite, or the like). The composition can be produced by compounding the raw material components and mixing and kneading the compounded substance in molten state. The obtained composition generates little toxicity in combustion, has high flame-retardancy, keeps the preferable properties of a base resin, has faint color tone and excellent moisture-resistance and moldability and gives a molded article having excellent gloss and appearance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has low toxicity and excellent flame retardancy and does not impair the properties and processability of the resin, especially without screw adhesion or generation of decomposition gas during granulation or molding. And a flame-retardant resin composition.

[0002]

2. Description of the Related Art Thermoplastic resins have the property of being easily ignited and flammable. For this reason, it cannot be used as it is for an inconvenient use when burning. Therefore, various flame retardants have been applied for use in such applications.

[0003] In general, flame retardation of a thermoplastic resin is performed by blending various flame retardants. Flame retardants are broadly classified into halogen-based flame retardants and non-halo-based flame retardants.

[0004] Halogen-based flame retardants have been pointed out to be toxic by acid gases such as hydrogen bromide and hydrogen chloride generated during combustion, and recently there has been a concern that dioxin may be generated. I have. For this reason, non-halogen flame retardants have attracted attention.

[0005] Examples of non-halogen flame retardants include metal hydroxides such as magnesium hydroxide. However, compared to halogen flame retardants, the gas generated during combustion is less toxic, but the flame retardancy is poor. There's a problem. Therefore, in order to make the resin flame-retardant, it must be incorporated in a large amount in the resin, which causes a problem that the properties of the resin are impaired.

In such a background, the present inventors have
Previously, a composition in which a sulfate of a triazine compound was blended with a thermoplastic resin as a non-halogen flame retardant material (Japanese Patent Application Laid-Open No.
No.-48812). Further, Japanese Patent Application Laid-Open No. 7-179
No. 674 and JP-A-6-336536 propose a composition in which phosphinic acid and a nitrogen compound are blended in a polyolefin, and US Pat. No. 5,344,866 discloses a composition in which vermiculite and glass fibers are blended in a thermoplastic resin. A flame-retardant resin composition is disclosed. However, although these compositions show a considerable combustion suppressing effect, the flame retardancy was not yet sufficient.

[0007]

SUMMARY OF THE INVENTION The present inventors have further developed a thermoplastic resin (hereinafter referred to as a thermoplastic resin) which realizes a high flame retardancy of V-0 in the UL94 standard and has a good color tone. I) at least one member selected from the group consisting of 100 parts by weight, a nitrogen-based flame retardant having no halogen atom, a phosphorus-based flame retardant having no halogen atom, and a nitrogen-phosphorus-based flame retardant having no halogen atom. Proposed a flame-retardant resin composition comprising 10 to 300 parts by weight of a kind of flame retardant (II) and 1 to 100 parts by weight of a hydrous phyllosilicate (III) represented by vermiculite (Japanese Patent Application No. Hei 10 (1998) -108).
No. 118680). JP-A-10-60160 proposes a flame-retardant resin composition in which a phosphorus-based flame retardant and a layered silicate are blended with a thermoplastic resin. As the phosphorus-based flame retardant, a phosphate ester-based flame retardant is proposed. Examples include flame retardants, phosphonitrile flame retardants, and polyphosphoric acid flame retardants, and vermiculite is exemplified as the layered silicate.

The flame-retardant resin composition using such a phosphorus-based flame retardant and vermiculite in combination has high flame retardancy and excellent color tone, and is useful.
Phosphorus-based flame retardants specifically exemplified in JP-A-118680 and JP-A-10-60160 are heat-resistant at the time of melt-kneading and molding like phosphate-based flame retardants of nitrogen-containing compounds such as amines. Were not sufficient, or had a low melting point such as a phosphate ester-based flame retardant or a phosphonitrile-based flame retardant, or were water-soluble and inferior in moisture resistance such as a polyphosphoric acid-based flame retardant. Therefore, in the flame-retardant resin compositions shown in these, if the flame retardant is inferior in heat resistance, the decomposition product of the flame retardant adheres to the screw during molding and makes stable molding or granulation difficult, Generation of decomposition gas was occurring. Also, when the flame retardant has a low melting point, the problem of adhesion of the flame retardant to the screw and dispersibility of the flame retardant occurs,
Further, even when the flame retardant is water-soluble, the above-mentioned moldability problem occurs due to moisture absorption during molding, or the molded article does not have sufficient moisture resistance and the surface is whitened over time, so there is room for improvement. there were.

[0009] Therefore, it has been a major problem to improve the flame-retardant resin composition using the above-mentioned phosphorus-based flame retardant and vermiculite in combination to further improve the moldability and the moisture resistance of the molded article.

[0010]

Means for Solving the Problems The present inventors have intensively studied in view of the above problems. As a result, they have found that the above-mentioned problems can be solved by using an aromatic organic phosphonic acid amine salt as a flame retardant, and have completed the present invention.

That is, the present invention is a flame-retardant resin composition comprising 100 parts by weight of a thermoplastic resin, 20 to 150 parts by weight of an amine salt of an aromatic organic phosphonic acid, and 0.1 to 50 parts by weight of a hydrous phyllosilicate. .

As the thermoplastic resin used in the present invention, known resins are used without any particular limitation. Examples include thermoplastic resins such as polyolefin-based resins, polystyrene-based resins, polyvinyl-based resins, polyamide-based resins, polyester-based resins, polycarbonate-based resins, and polyether-based resins, and various resins modified from these. .

Here, as the polyolefin resin,
Examples include α-olefin homopolymers such as ethylene, propylene, butene, hexene, 4-methylpentene and octene, and copolymers of two or more α-olefins. Typical examples of the polyolefin resin in the present invention include polypropylene resins such as propylene homopolymer, propylene-ethylene random copolymer, and propylene-ethylene block copolymer; low-density polyethylene, high-density polyethylene And polyethylene-based resins such as ethylene-α-olefin random copolymer, propylene-ethylene-butene copolymer and the like.

As the polystyrene resin, polystyrene, acrylonitrile-styrene copolymer (A
S), acrylonitrile-butadiene-styrene copolymer (ABS) and the like.

Examples of the polyvinyl resin include homopolymers of vinyl monomers such as alkyl acrylate, alkyl methacrylate, vinyl acetate and vinyl alcohol, and copolymers of these vinyl monomers with the above-mentioned α-olefin. And the like.

Further, polyamide-based resins include nylon 6, nylon 6,6 and the like, and polyester-based resins include polyethylene terephthalate (PE).
T), polyalkene terephthalate represented by polybutylene terephthalate (PBT); polyalkene adipate; polylactone; polyhydroxycarbonate.

Further, as the polycarbonate resin,
Resins having an aromatic carbonate as a constituent unit, such as poly-4,4'-dioxydiphenyl-2,2-propane carbonate, may be mentioned. Examples of polyether resins include polyphenylene ether and polyethylene ether. Is mentioned.

In the present invention, these thermoplastic resins may be either plastomers or elastomers.
Examples of the elastomer include an ethylene-propylene-butadiene copolymer, a styrene-butadiene copolymer (SBR), and a nitrile-butadiene copolymer (NB
R), polybutadiene, polyisoprene and the like.

These thermoplastic resins can be used alone or in combination of two or more. Further, a modified product of the above-described thermoplastic resin, for example, the thermoplastic resin is grafted with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, or siloxane, or a siloxane. A modified product obtained by the above method can also be used.

Among the above thermoplastic resins, polyolefin resins are preferred because they are versatile and can provide molded articles having excellent chemical resistance and flame retardancy. In particular, polypropylene-based resins such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, and the like, the flame-retardant resin composition of the present invention obtained using these resins has moldability, It is preferable in the present invention because it gives a molded article excellent in mechanical strength, heat resistance, appearance and cost performance.

In the flame-retardant resin composition of the present invention, an aromatic organic phosphonic acid amine salt is blended with the thermoplastic resin. These aromatic organic phosphonic acid amine salts usually have a decomposition temperature of 270 ° C. to 450 ° C. and a thermogravimetric measurement (T
The weight loss from 200 ° C. to 250 ° C. measured in G) is 5
% Or less. Also, the melting point is higher than the decomposition temperature. Therefore, during molding of the thermoplastic resin, which is generally melt-kneaded at 150 ° C. to 250 ° C., since these are hardly decomposed and are in a solid state, they are easily dispersed, and the decomposed product adheres to the screw of the melt-kneader. No decomposition gas is generated.

The amine salt of an aromatic organic phosphonic acid has a weight loss of at least 20% from 300 ° C. to 500 ° C. measured by thermogravimetry (TG) from the decomposition temperature. Therefore, since the decomposition temperature is lower than the decomposition temperature of the thermoplastic resin, when the resin is exposed to high temperatures,
The resin decomposes faster than it decomposes to form a polyphosphoric acid compound to form a heat-resistant film. Further, the mechanism of promoting carbonization by the solid acid is well exhibited and a flame retardant effect is exhibited.

Furthermore, these amine salts of aromatic organic phosphonic acids are hardly soluble in water and have low hygroscopicity, so that the appearance of molded articles does not deteriorate due to moisture absorption after molding.

In the present invention, such an aromatic organic phosphonic acid amine salt is an amine salt of an aromatic organic phosphonic acid in which a hydrogen atom directly bonded to a phosphorus atom of phosphonic acid is substituted with an aromatic group. An amine salt of an aromatic organic phosphonic acid represented by the formula H ₂ PArO ₃ (where Ar is an aryl group). Here, Ar is an aryl group, specifically, a phenyl group, a naphthyl group, or the like. In these aryl groups, an alkyl group such as a methyl group or an ethyl group, an alkylene group such as a vinyl group or an allyl group, a substituent such as an amino group, a hydroxyl group, or an alkoxy group may be introduced into an aromatic ring. .

The aromatic organic phosphonic acid forming the amine salt may be one in which a plurality of phosphonic acid groups are bonded to a polyvalent aromatic group such as an arylene group. In particular,
Phenylenebisphosphonic acid and the like.

The amines which form salts with the aromatic organic phosphonic acids include aliphatic amine compounds such as ethylamine, diethylamine, ethanolamine and diethanolamine; aromatic amine compounds such as aniline and phenylenediamine; pyridine, melamine and isocyanuric acid. And a salt with a nitrogen-containing heterocyclic compound.

In particular, the amine is represented by the following formula (R ² ) ₂ N—R ¹ — (NH—R ¹ ) _n —N (R) because it can provide a composition having excellent flame retardancy and moisture resistance. ² ) _{2 wherein} R ¹ is the same or different alkylene group, R ² is the same or different alkyl group or hydrogen, and n is an integer of 0 to 5. Multivalent amine compounds are preferred. Here, the alkylene group of R ¹ preferably has 1 to 5 carbon atoms, and particularly preferably has 2 or 3 carbon atoms such as an ethylene group.
The alkyl group of R ² is preferably a group having 1 to 3 carbon atoms such as a methyl group and an ethyl group. Specific examples include ethylenediamine, diethylenetriamine, 1,3-diaminopropane, N, N, N ′, N′-tetramethylethylenediamine, and the like, with ethylenediamine being particularly preferred.

Further, the amine forming the salt is represented by the following formula for the same reason as described above.

[0029]

Embedded image

(However, R^ThreeAre the same or different
Hydrogen, alkyl group, aryl group, amino group, hydroxy
, Alkoxy, or mercapto)
Nitrogen-containing heterocyclic compounds having a triazine skeleton are preferred.
Good. Where R ^ThreeIn the above, the alkyl group is methyl
Group, ethyl group, propyl group, butyl group, etc.
Are preferable, and the aryl group is a phenyl group, tolyl
Having 6 to 10 carbon atoms such as a group, xylyl group, naphthyl group, etc.
Preferably, the alkoxy group is a methoxy group, ethoxy
Having 1 to 4 carbon atoms, such as group, propoxy group, butoxy group
Is preferred. Specifically, triazine, melamine, ben
Zoguanamine, methylguanamine, cyanuric acid, trime
Tilt triazine, triphenyl triazine, amelin,
Amelide, thiocyanuric acid, diaminomercaptotria
Gin, diaminomethyltriazine, diaminophenylt
Liadin, diaminoisopropoxytriazine, etc.
Can be

In the present invention, examples of the aromatic organic phosphonic acid amine salts which are particularly preferably used include phenylphosphonic acid ethylenediamine salt, phenylphosphonic acid melamine salt, tolylphosphonic acid ethylenediamine salt, phenylenebisphosphonic acid ethylenediamine salt, tolylphosphonic acid ethylenediamine salt. Acid melamine salt, phenylphosphonic acid 1,3-diaminopropane salt, phenylphosphonic acid triazine salt, phenylphosphonic acid ameline salt, phenylphosphonic acid diaminomercaptotriazine salt, phenylphosphonic acid diaminomethyltriazine salt, phenylphosphonic acid diaminoisopropoxytriazine And benzoguanamine salts of phenylphosphonic acid. Among them, phenylphosphonic acid ethylenediamine salt, phenylphosphonic acid melamine salt, and tolylphosphonic acid ethylenediamine salt are preferred, and phenylphosphonic acid ethylenediamine salt is particularly preferred.

Since the aromatic organic phosphonic acid is a dibasic acid, the above-mentioned amine salts of aromatic organic phosphonic acid include those having one bonded amine and those having two bonded amines. Any can be used without restriction.
These aromatic organic phosphonic acid amine salts can be used alone or in combination.

In the present invention, the compounding amount of the amine salt of the aromatic organic phosphonic acid is 20 to 150 parts by weight, preferably 25 to 100 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the amount is less than the lower limit, a sufficient flame retardant effect cannot be obtained, and if the amount is more than the upper limit,
Not only is there a decrease in moldability, impact resistance, an increase in specific gravity, and the like, but also disadvantageous in that stable kneading work becomes difficult.

The flame-retardant resin composition of the present invention further contains a hydrous phyllosilicate. The hydrous phyllosilicate is a silicate in which tetrahedrons of Si—O are bonded to each other to form a layer, which is a basic structure.
It contains water or water of crystallization between layers and has the property of expanding when heated. Even if the aromatic organic phosphonic acid amine salt is used alone, the thermoplastic resin composition does not have high flame retardancy, but is used in combination with the hydrous phyllosilicate having such expandability. By doing so, the flame retardancy is greatly improved, and the resin composition has excellent flame retardancy.

As the hydrated phyllosilicate, vermiculite, hydrobiotite and the like are known, and known phyllosilicates can be used without any limitation. Vermiculite is particularly preferably used.

Such a hydrous phyllosilicate has a particle size of 0.1.
Those having a thickness of 1 to 500 μm are generally used. The composition of the present invention using the hydrated phyllosilicate having an average particle size in the above range is particularly excellent in mechanical strength, and since the layered structure of hydrated phyllosilicate is retained, a molding exhibiting a high flame retardant effect is obtained. Give goods. The average particle size of the hydrous phyllosilicate is 1 to 100 μm
m, more preferably 5 to 50 μm. As described above, the molded article obtained from the composition of the present invention using the hydrous phyllosilicate having a small average particle diameter has excellent surface gloss, and the blended hydrous phyllosilicate particles are inconspicuous on the surface of the molded article. Presents an excellent appearance.

Further, it is preferable that the water content of the hydrous phyllosilicate is retained at the time of kneading the composition, and is sufficiently vaporized at a temperature at which the flame retardant effect is exhibited. Therefore,
The hydrated phyllosilicate has a weight reduction rate of 2% or more when heated from 200 ° C. to 900 ° C. measured according to thermogravimetry (TG), and more preferably 3 to 20%. Those are particularly excellent in the flame retardant effect and are suitable.

In order to make the hydrous phyllosilicate have the above-mentioned water content and particle size, known pulverization and classification methods can be adopted. Among them, a method of pulverizing by impact such as a hammer mill, a pin mill, and a jet mill is preferable. Even better results can be obtained by crushing while keeping the temperature of the crushed particles below 80 ° C.

In the present invention, the amount of the hydrated phyllosilicate is 0.1 to 5 parts by weight per 100 parts by weight of the thermoplastic resin.
0 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight. When the blending amount of the hydrous phyllosilicate is in the above range, a remarkable improvement in the flame retardant effect and good surface appearance and mechanical properties can be obtained.

The flame-retardant resin composition of the present invention contains a silicone-based anti-drip agent represented by silicone powder, silicone resin, silicone gum, etc., and an anti-drip agent such as tetrafluoroethylene, scaly filler, and phenol resin. It can also be added.

Further, the flame-retardant resin composition may contain conventionally known additive components, if necessary, in addition to the components described above, as long as the effects of the present invention are not impaired. Examples thereof include antioxidants (phenol-based, phosphine-based, thioether-based, etc.), weathering agents (benzophenone-based, salicylate-based, benzotriazole-based, hindered amine-based, etc.), metal deactivators, halogen scavengers, lubricants ( Olefins, fatty acids and their derivatives), crystallization nucleating agents (metal salts, talc, sorbitol, etc.), fillers (talc, calcium carbonate, barium sulfate, glass fiber, etc.), blooming inhibitors, anti-blocking agents, Clouding agents, adhesives, coloring agents, matting agents, antistatic agents,
Examples include oxygen and carbon dioxide gas absorbents, gas adsorbents, freshness preserving agents, enzymes, deodorants, and fragrances.

The flame-retardant resin composition of the present invention can be obtained by mixing components and mixing and melt-kneading them. There are no particular restrictions on the order of mixing the components, the method of kneading, and the like. For example, the method of mixing may be a conventional method using a tumbler blender, V-type blender, Henschel mixer, ribbon mixer, or the like. Further, the method of melt kneading is not particularly limited, generally a screw extruder,
It is preferable to use a Banbury mixer, a mixing roll or the like at a temperature higher than the melting point of the thermoplastic resin. This melt-kneading can also be performed under an inert gas flow such as nitrogen gas.

[0043]

The flame-retardant resin composition of the present invention has low toxicity during combustion and high flame retardancy because the compounded flame retardant is a non-halogen flame retardant. Therefore, the properties of the resin serving as the base material are well maintained,
It is excellent in that the color tone is pale (pale yellow). further,
This excellent flame retardancy is exhibited well even when the average particle size of the hydrated phyllosilicate compounded is within the range of 5 to 50 μm, so that a molded article excellent in gloss and appearance can be obtained. Is possible.

In the flame-retardant resin composition, the flame-retardant and its decomposed products do not adhere to the screw of the melt-kneader at the time of melt-kneading, and no decomposition gas of the flame-retardant is generated. Granulation and molding can be performed stably. Furthermore, after molding, the appearance of the molded article does not deteriorate due to moisture absorption.

Therefore, the flame-retardant resin composition of the present invention can be used for various applications requiring flame retardancy. Examples of such molded articles include various electric products (washing machines, refrigerators, dish dryers, rice cookers, electric fans, ventilation fans, televisions,
Parts and covers for personal computers, stereos, telephones, microwave ovens, heating toilets, irons, etc .; Parts and covers for photothermal equipment (air conditioners, stoves, stoves, fan heaters, water heaters); interior and exterior materials for buildings; automobiles , Ships, aircraft, etc., or interior materials.

[0046]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, measurements and tests were performed as follows.
It carried out by the following method.

(1) Measurement method and test method Average particle size SK LASER manufactured by Seishin Enterprise Co., Ltd.
The measurement was carried out using MICRON Sizer PRO-7000S with the solvent methanol.

Thermogravimetric Measurement Using a differential thermal analysis / thermogravimetric measuring device, TG / DTA200 manufactured by Seiko Denshi Kogyo Co., Ltd., a nitrogen gas flow of 200 m
1 / min, from 30 to 950 ° C., heating rate 40
The temperature change was measured at a temperature of 950 ° C./minute, and the weight change was measured under the condition of maintaining the temperature at 950 ° C. for 10 minutes.

In the TG analysis, the weight loss (in percent) of the aromatic organic phosphonic acid amine salt in the temperature range from 200 ° C. to 250 ° C. and from 300 ° C. to 500 ° C. was determined. In addition, hydrous phyllosilicate is
The weight loss in the temperature range from 200 ° C. to 900 ° C. was determined.

Evaluation of Moldability After continuing granulation for 1 hour with a vented Φ30 mm extruder,
The extruder was disassembled, the screw was pulled out, and the state of adhesion of foreign substances on the screw surface was observed.

；: No change at all.

Δ: Slight sticking is observed.

X: Sticking is clearly observed. Or burning is recognized.

Flammability Test A test piece having a length of 5 inches, a width of イ ン チ inch and a thickness of 1/8 inch was evaluated for flammability by a vertical burning test in accordance with the UL94 standard.

Moisture Resistance Test A test piece having a length of 5/2 inch, a width of 3/2 inch and a thickness of 1/8 inch was subjected to a test at a temperature of 60 ° C. and a humidity of 90%.
After standing for a day, the surface was visually observed and evaluated on a three-point scale.

○: No change at all.

Δ: Partial slight whitening is observed.

X: Whitening is clearly observed.

Color Test Using J50E-P manufactured by Nippon Steel Works, Ltd., 80 mm ×
A test piece of 47.5 mm × 3 mm was molded, and its color tone was visually evaluated.

Surface appearance test Using J50E-P manufactured by Nippon Steel Works, 80 mm ×
A test piece of 47.5 mm × 3 mm was molded, and its surface appearance was visually compared. The results were evaluated according to the following criteria.

；: The gloss was good, and no compound particles were observed.

Δ: The gloss is good, but the compound particles are visible.

X: Poor gloss, and compound particles were visually recognized. Or, the surface is severely rough.

The symbols shown in Examples and Comparative Examples are as follows.

Thermoplastic resin PP1: Ethylene-propylene block copolymer (Tokuyama polypro PN670G (Tokuyama Co., Ltd.)) PP2: Propylene homopolymer (Tokuyama polypro PN1)
50G (Tokuyama Corporation)) HDPE: High-density polyethylene (Suntech HD-J3)
10 (Asahi Kasei Corporation)) PS: polystyrene (Estyrene G-20 (Nippon Steel Chemical Co., Ltd.)) ABS: ABS (Psycholac AM-11001 (Ube Sicon)) The flame retardants used are as follows: Was prepared.

Amine salt of aromatic organic phosphonic acid Ethylenediamine phenylphosphonate: A 10% aqueous solution of ethylenediamine was added dropwise while stirring a 10% aqueous solution of phenylphosphonic acid, and when 1/2 mole amount was added, the precipitated precipitate was removed. It was filtered off, dried and pulverized in a lab mill. The weight loss in the temperature rise range from 200 ° C. to 250 ° C. measured by thermogravimetry (TG) is 0%, 300%.
76% weight loss in temperature range from ℃ to 500 ℃
Met. Also, no melting point peak was observed at a temperature lower than the start of decomposition.

Melamine salt of phenylphosphonic acid: An equimolar amount of a 10% aqueous solution of melamine is added to a 10% aqueous solution of phenylphosphonic acid, stirred at 80 ° C. for 6 hours, and the precipitate is filtered off, dried and pulverized by a lab mill. did. The weight loss in the temperature range from 200 ° C. to 250 ° C. measured by thermogravimetry (TG) is 0%, and the weight in the temperature range from 300 ° C. to 500 ° C. measured by thermogravimetry (TG). The decrease was 53%. Also, no melting point peak was observed at a temperature lower than the start of decomposition.

Ethylenediamine tolylphosphonic acid salt: A 10% aqueous solution of ethylenediamine was added dropwise while stirring a 10% aqueous solution of tolylphosphonic acid, and when 1/2 mole amount was added, the deposited precipitate was separated by filtration, dried, and dried in a laboratory mill. And crushed. From 200 ° C measured by thermogravimetry (TG) to 2
The weight loss in the temperature rising range up to 50 ° C. was 0%, and the weight loss in the temperature rising range from 300 ° C. to 500 ° C. measured by thermogravimetry (TG) was 79%. Also, no melting point peak was observed at a temperature lower than the start of decomposition.

Other phosphorus compounds Phenylphosphonic acid; measured by thermogravimetry (TG), Wako Pure Chemical Industries, Ltd.
Weight loss in the temperature rise range from 00 ° C to 250 ° C is 1
%, From 300 ° C. to 500 measured by thermogravimetry (TG)
The weight loss in the temperature range up to ° C was 49%. The melting point was 165 ° C.

Ethylenediamine phosphate salt: A 10% aqueous solution of ethylenediamine was added dropwise while stirring a 10% aqueous solution of phosphoric acid, and when an equimolar amount was added, the deposited precipitate was separated by filtration, dried, and pulverized in a laboratory mill. The weight loss in the temperature range from 200 ° C. to 250 ° C. measured by thermogravimetry (TG) is 13%, and the weight in the temperature range from 300 ° C. to 500 ° C. measured by thermogravimetry (TG). The decrease was 29%. Also, no melting point peak was observed at a temperature lower than the start of decomposition.

Diaminocyclohexane phosphate: A 10% aqueous solution of diaminocyclohexane was added dropwise while stirring the 10% aqueous solution of phosphoric acid.
The deposited precipitate was separated by filtration, dried, and pulverized by a lab mill.
The weight loss in the temperature range from 200 ° C. to 250 ° C. measured by thermogravimetry (TG) was 6%, and the thermogravimetry (T
The weight loss in the temperature range from 300 ° C. to 500 ° C. measured in G) was 37%. Also, no melting point peak was observed at a temperature lower than the start of decomposition.

Phenoxyphosphazene; Otsuka Chemical Co., Ltd., melting point 100 ° C.

Phosphonic acid ethylenediamine salt: A 10% aqueous solution of ethylenediamine was added dropwise while stirring a 10% aqueous solution of phosphonic acid.
After concentrating to / 5 volume, the deposited precipitate was separated by filtration, dried and pulverized by a lab mill. 2 measured by thermogravimetry (TG)
Weight loss in the temperature rise range from 00 ° C to 250 ° C is 7
%, From 300 ° C. to 500 measured by thermogravimetry (TG)
The weight loss in the temperature range up to ° C was 32%. Also, no melting point peak was observed at a temperature lower than the start of decomposition.

Triphenyl phosphate; Wako Pure Chemical Industries, Ltd., melting point: 50 ° C. Ammonium polyphosphate; While a 10% aqueous solution of polyphosphoric acid is being stirred, an aqueous 10% ammonium solution is added dropwise to 100 parts by weight of polyphosphoric acid. At the time of adding 22 parts by weight, the mixture was cooled to 4 ° C., and the deposited precipitate was separated by filtration, dried and pulverized by a lab mill. The weight loss in the temperature range from 200 ° C. to 250 ° C. measured by thermogravimetry (TG) is 0%, and the weight in the temperature range from 300 ° C. to 500 ° C. measured by thermogravimetry (TG). The reduction was 22%. Also, no melting point peak was observed at a temperature lower than the start of decomposition.

-Hydrated phyllosilicate vermiculite (30 μm): Unfired No. 0 product from South Africa was pulverized by an impact mill. The average particle size was 30 μm, and the weight loss in the temperature rising range from 600 ° C. to 800 ° C. measured by thermogravimetry (TG) was 2.1%.

Vermiculite (12 μm): Unfired South Africa product No. 0 was pulverized by an impact mill. The average particle size was 12 μm, and the weight loss in the temperature rising range from 600 ° C. to 800 ° C. measured by thermogravimetry (TG) was 1.9%.

Blowing agent azodicarbonamide; Wako Pure Chemical Industries, Ltd. Ammonium bicarbonate; Wako Pure Chemical Industries, Ltd. Examples 1 to 12 In addition to the composition shown in Table 1, based on 100 parts by weight of thermoplastic resin 2,6-t-butyl-4-methylphenol (Stabilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.): 0.1 parts by weight, dilauryl thiodipropionate (Sumitomo Chemical Co., Ltd., stabilizer TPL-R) ): 0.2 parts by weight, and 0.1 parts by weight of calcium stearate (manufactured by Dainippon Ink and Chemicals, Inc.) were added and preliminarily mixed with a Henschel mixer. Then, using a vented φ30 mm extruder, the obtained flame-retardant resin composition was heated to a resin temperature of 185.
The mixture was extruded in the form of a strand at ℃, cooled in a water bath, cut into about 5 mm and dried to obtain pellets. Next, the pellets were formed into various test pieces by a 50-ton injection molding machine.

A flammability test and a moisture resistance test were performed for each composition, and the results are shown in Table 2.

[0079]

[Table 1]

[0080]

[Table 2]

Comparative Examples 1 to 13 The procedure of Example 1 was repeated, except that the composition of Table 1 to be added to the thermoplastic resin was changed to the composition of Table 3. The results are shown in Table 4.

[0082]

[Table 3]

[0083]

[Table 4]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AC021 BB021 BB121 BB141 BB151 BB171 BB201 BC021 BE021 BF021 BG031 BN001 BN151 BP021 CF051 CF181 CG011 CH021 CH071 CL001 DJ007 EW126 FD010 FD136 FD137 FD200 G

Claims (2)

[Claims] 1. A flame-retardant resin composition comprising 100 parts by weight of a thermoplastic resin, 20 to 150 parts by weight of an amine salt of an aromatic organic phosphonic acid and 0.1 to 50 parts by weight of a hydrous phyllosilicate. 2. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a polypropylene resin.