JPH09183864A - Flame-retardant and flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant useful as electric/electronic parts, etc., excellent in bleed resistance, having fixed thermal stability and solubility, comprising a specific repeating unit. SOLUTION: This flame-retardant substantially comprises a phosphazene polymer having a repeating unit shown by the formula, has a temperature of 10wt.% loss in weight in a heating test (10 deg.C/minute heating rate) of >=200 deg.C as an index of thermal decomposition temperature and <=10wt.% solubility in water and methanol at 20 deg.C. A thermoplastic resin such as a polyester or a polyethylene in an amount of 100 pts.wt. is mixed with 1-100 pts.wt. of the phosphazene polymer to give the objective flame-retardant resin composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant and a flame retardant resin composition using a phosphazene polymer. More specifically, it has excellent flame retardancy, and there is little coloring or decomposition of the flame-retardant resin composition with the flame-retardant agent, or less elution of the flame-retardant agent in the hydrolysis test of the resin resin composition, such as connectors, relays, switches, case members, and transformers. TECHNICAL FIELD The present invention relates to a flame-retardant resin composition suitable for members, electric / electronic device parts such as coil bobbins, automobile parts, machine parts, and building materials, and a flame retardant used for the same.

[0002]

2. Description of the Related Art Polyester typified by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, liquid crystal polyester, or polycarbonate, polyamide, polyphenylene oxide, polyphenylene sulfide and polyethylene, polypropylene, polystyrene, ABS, etc. The thermoplastic resins such as polyolefins are being used as injection molding materials in a wide range of fields such as machine mechanism parts, electric parts, and automobile parts by taking advantage of their excellent characteristics. On the other hand, since these thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary into the resin is generally used. However, this method has a problem that a large amount of smoke is generated during combustion.

Accordingly, in recent years, it has been strongly desired to use a flame retardant containing no halogen in order to overcome the disadvantages of these halogen-based flame retardants.

Heretofore, a blend of a phosphorus compound has been known as a method for making a thermoplastic resin flame-retardant without using a halogen-based flame retardant. For example, techniques for blending red phosphorus to make it flame-retardant are disclosed in JP-A-49-74240, JP-A-6-80885, and JP-A-5-287119. A technique for blending polyphosphoric acid amide to make it flame-retardant is disclosed in Japanese Patent Application Laid-Open No. 7-138463.

The phosphazene polymer, a method for producing the same, and a resin composition containing the phosphazene polymer are described in German Patent No. 2317282, US Pat. No. 2,642,405, US Pat. No. 2,661,341, and US Pat. No. 2661263, U.S. Pat. No. 2,648,597, U.S. Pat. No. 2,661,342.
Specification, US Pat. No. 266136, JP-A-5
No. 0-46760.

[0007]

A flame-retardant resin composition for injection molding, particularly for mechanical parts, electric / electronic parts and automobile parts, has not only excellent flame retardancy of molded products but also thermal stability of polymer. Stability and color stability are required. However, the conventional method of blending red phosphorus and polyphosphoric acid amide can impart a flame retardant effect, but these compounds cause the resin composition to be severely colored or decomposed, or the resin composition to penetrate into an aqueous solution. In that case, there was a problem that these compounds would be eluted. Further, the phosphazene polymer obtained by the conventional technique has thermal stability,
Heat resistance and solvent resistance are poor, and when the phosphazene is blended with a resin, flame retardancy can be imparted, but since the thermal stability of the phosphazene polymer is poor, the resin composition is colored, decomposes, or has a resin composition. However, there is a problem that the phosphazene polymer is eluted when it is permeated into an aqueous solution.

[0008]

The inventors of the present invention have made extensive studies in view of the above situation, and as a result, a flame retardant composed of a specific phosphazene polymer is excellent in non-coloring property, thermal stability and solvent resistance. In addition, a resin composition containing a phosphazene polymer is excellent in flame retardancy, and there is little coloring or decomposition of the resin composition, and further less elution of the flame retardant when the resin composition is penetrated into a solvent. Found and arrived at the present invention.

That is, the present invention consists essentially of a repeating unit represented by the following general formula (1), and is a heating test in nitrogen which is an index of the thermal decomposition temperature (heating rate 10 ° C./min).
In 100 parts by weight, the flame retardant and the thermoplastic resin copolymer 100 made of a phosphazene polymer having a temperature of 200 ° C. or more and a solubility in water and methanol of 10% by weight or less at 20 ° C. 10 parts by weight in a heating test in nitrogen (temperature rising rate 10 ° C./min), which is substantially composed of a repeating unit represented by the following general formula (1), relative to parts by weight and is an index of thermal decomposition temperature. %
A flame-retardant resin composition comprising 1 to 100 parts by weight of a phosphazene polymer having a temperature of 200 ° C. or more and a solubility in water and methanol of 10% by weight or less at 20 ° C. Is.

[0010]

Embedded image

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphazene polymer according to the present invention is essentially a repeating unit represented by the above formula (1), and is a cyclic substance in which the polymer ends are covalently bonded. May be. In the polymer, the general formula (1)
Other repeating units other than may be contained,
The unit represented by (1) is 50 with respect to the phosphazene polymer.
It is preferably at least mol%, more preferably 7
0 mol% or more.

Examples of the repeating unit other than the unit represented by (1) include the repeating unit represented by the following general formula (2), but these structures are not particularly limited. That is, in a heating test in nitrogen which is an index of the thermal decomposition temperature of the phosphazene polymer (heating rate 10 ° C./min), the temperature when the weight is reduced by 10% by weight is 200 ° C. or higher and at 20 ° C. If the solubility in water and methanol is 10% by weight or less, the repeating structure other than the unit represented by (1) is not particularly limited.

[0013]

Embedded image (X represents a hydroxy group, a chloride, an amine, and a secondary amine, and the secondary amine may form a crosslinked structure.) The phosphazene polymer in the present invention has a heat measured by a thermogravimetric analyzer (TGA). 10 in a heating test in nitrogen (a temperature rising rate of 10 ° C./min), which is an index of the decomposition temperature
The temperature at the time of weight reduction is preferably 200 ° C or higher, preferably 300 ° C or higher, and more preferably 3 ° C.
It is 50 ° C or higher. When the temperature is lower than 200 ° C., the phosphazene polymer generates a decomposition gas when the resin is melt-kneaded with the phosphazene polymer, or when the resin composition is molded, processed and melt-spun, or decomposes the resin by the decomposition gas. Is caused, which is not preferable.

The phosphazene polymer of the present invention is 20
Solubility in water and methanol at 10 ° C is 10
It is not more than 8% by weight, preferably 8% by weight, more preferably 5% by weight.

The solubility in water and methanol is 2
The solubility of 1 g of the phosphazene polymer in 100 ml of water at 0 ° C. is shown. Usually, 1 g of the phosphazene polymer is suspended or dissolved in 100 ml of water and methanol, stirred for 6 hours at 20 ° C., the soluble portion is recovered by filtration, and dried under vacuum at 100 ° C. to obtain water and methanol. The phosphazene polymer soluble in water is weighed. From this value, solubility = weight of soluble part / 1 g × 100
Was calculated and the solubility was used as an index of solvent resistance.

In the phosphazene polymer, a heating test in nitrogen, which is an index of the solubility in water and methanol and the thermal decomposition temperature (heating rate 10 ° C./minute).
In the above, it is considered that the temperature when reducing the amount by 10% by weight reflects the degree of polymerization of the phosphazene polymer.

Such a phosphazene polymer can be produced by the following method.

That is, phosphorus oxychloride is reacted with ammonia gas or an aqueous ammonia solution in a solvent or without a solvent at a polymerization temperature of 100 ° C. or lower, and after a predetermined amount of ammonia is added, polymerization is further performed at a temperature of 100 ° C. or higher and 200 ° C. or lower. The reaction product obtained was allowed to stand at 200 ° C. under reduced pressure.
It can be produced by stabilizing at 400 ° C. or lower.

The phosphorus oxychloride of the present invention may be a commercially available product. A commercially available product may be used as it is, or it may be distilled under a nitrogen atmosphere and used.

The ammonia gas or aqueous ammonia solution of the present invention is not particularly limited, and commercially available products can be used. Since commercially available ammonia gas contains a small amount of water, the ammonia gas can be used after being dehydrated by passing it through a water absorbing compound such as molecular sieves, potassium hydroxide or sodium hydroxide. When an aqueous ammonia solution is used, the aqueous ammonia solution may be used as it is for the reaction with phosphorus oxychloride, but from the viewpoint of the thermal stability of the polymer obtained, the aqueous ammonia is boiled,
It is preferable to use volatile ammonia gas. At this time, the volatilized ammonia gas may be recovered before use, or the volatilized ammonia gas may be used as it is for the reaction with phosphorus oxychloride. Further, the volatilized ammonia gas can be used after being dehydrated by passing it through a water-absorbing or hygroscopic compound such as molecular sieves, potassium hydroxide or sodium hydroxide.

The use amount of phosphorus oxychloride and ammonia gas or aqueous ammonia solution is usually 1-fold mole or more and 10-fold mole or less, preferably 2-fold mole or more and 6-fold mole or less, relative to 1-fold mole of phosphorus oxychloride. More preferably, the amount is 2 times or more and 4 times or less.

When an aqueous ammonia solution is used,
The amount of ammonia gas contained in the used aqueous ammonia solution is regarded as the actual amount of ammonia.

The reaction temperature of the phosphorus oxychloride and ammonia of the present invention is 100 ° C. or lower, preferably 90 ° C.
Hereafter, it is more preferably 80 ° C or lower. Within this temperature range, the reaction of phosphorus oxychloride and ammonia can be controlled to a preferable state.

The lower limit is not particularly limited, but is usually 0 ° C. or higher, preferably 10 ° C., from the economical aspect of the cooling process.
As described above, more preferably 20 ° C. or higher.

The reaction between the phosphorus oxychloride and ammonia can be carried out in a solvent or without a solvent. When carried out in a solvent, the solvent used is not particularly limited as long as it is a solvent that does not react with phosphorus oxychloride or ammonia,
Pentane, hexane, heptane, benzene, toluene,
Xylene, cyclohexene, cyclohexane, paraffin, liquid paraffin, tetralin, decalin, petroleum, kerosene, chlorobenzene, 1,2,4-trichlorobenzene, o-dichlorobenzene, p-dichlorobenzene, m
-Dichlorobenzene, diglyme, ethyl ether, tetrahydrofuran, pyridine etc. can be used.

The amount of the solvent used when using the solvent is not particularly limited, but from the viewpoint of suppressing the rapid polymerization reaction, suppressing the heat generation of the polymerization and economically, it is usually 0.1 L per 1 L of phosphorus oxychloride. Above 100L, preferably 0.2L
It is 10 L or less and more preferably 0.5 L or more and 5 L or less.

The addition rate of ammonia is not particularly limited, but since the reaction between phosphorus oxychloride and ammonia is an exothermic reaction, it is preferable to control the addition rate of ammonia so that the polymerization temperature does not exceed 100 ° C.

In the present invention, in the reaction of phosphorus oxychloride and ammonia, it is preferable to add a predetermined amount of ammonia gas or aqueous ammonia solution and then to carry out the reaction at a polymerization temperature of 100 ° C. or higher and 200 ° C. or lower.

The polymerization temperature at this stage is 100 ° C. or higher and 20
The temperature is 0 ° C or lower, preferably 120 ° C or higher and 200 ° C or lower, and more preferably 150 ° C or higher and 200 ° C or lower.

The polymerization time at this stage varies depending on the amount of solvent used or the polymerization temperature, but is usually 0.1 hours or more and 20 hours or less, preferably 0.5 hours or more and 10 hours or less, more preferably 1 hour or more 8 Less than an hour.

When a low boiling point solvent is used as the polymerization solvent, the low boiling point solvent may be distilled off at this stage, or ammonia gas or aqueous ammonia solution may be added and the reaction product may be filtered from the reaction solution. Alternatively, it may be separated from the solution by a method such as centrifugation.

The reaction product thus obtained can be used as it is in the next process.
Alternatively, at this stage, washing may be performed with an organic solvent having active hydrogen, water, or an alkaline aqueous solution.

As the organic solvent having active hydrogen, an organic solvent having a hydroxyl group such as methanol, ethanol and propanol and an organic solvent having an amino group such as ethylamine and ethanolamine can be used. The alkaline aqueous solution is not particularly limited as long as the pH is 7 or less, but an alkaline aqueous solution such as an aqueous ammonia solution, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.

When washed with an organic solvent having active hydrogen, water, or an alkaline aqueous solution, the recovered product can be further dried under reduced pressure. The reduced pressure drying conditions at this time are not particularly limited, but the degree of reduced pressure is usually 0.1 mmHg or more and 500 m or less.
mHg, preferably 0.1 mmHg or more 200
mmHg or less, more preferably 0.1 mmHg or more 1
It is not more than 00 mmHg.

The drying temperature at the time of drying under reduced pressure is not particularly limited, but is usually 20 ° C. from the viewpoint of the thermal stability of the obtained polymer.
Or more and 200 ° C or less, preferably 50 ° C or more and 180
C. or lower, more preferably 60 to 150.degree.

The reaction product thus obtained is further stabilized under reduced pressure at 200 ° C. or higher and 400 ° C. or lower to obtain a phosphazene polymer having excellent thermal stability and solvent resistance.

The stabilization temperature of the present invention is usually 20 from the viewpoint of thermal stability and solvent resistance of the obtained phosphazene polymer.
0 ° C to 400 ° C, preferably 200 ° C to 350 ° C, more preferably 200 ° C to 300 ° C
It is as follows.

By carrying out the heating reaction under reduced pressure, the thermal stability and solvent resistance of the phosphazene polymer are remarkably improved. Decompression degree is 0.1 mmHg or more and 100 mmH
g or less, preferably 0.1 mmHg or more and 50 mmH
g or less, more preferably 0.1 mmHg or more and 10 mm
Hg or less.

The phosphazene polymer thus obtained can be used as it is, or can be washed with water or an organic solvent and dried. Further, the obtained phosphazene polymer can be crushed and used.

The phosphazene polymer exhibits excellent performance as a flame retardant.

The thermoplastic resin in the flame-retardant resin composition of the present invention is a synthetic resin which exhibits fluidity when heated and can be molded by utilizing this. Specific examples thereof include polyester, liquid crystal polyester, polycarbonate, polyamide, wholly aromatic polyamide, wholly aromatic polyester, polyimide, polybenzimidazole, polyketone, polyether ether ketone, polyether ketone, polyether sulfone, and polyphenylene oxide. , Phenoxy resin, polyphenylene sulfide, phenol resin, phenol-formaldehyde resin, polypropylene, polyethylene, olefin polymers such as polystyrene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene Copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer And ethylene / propylene-g-maleic anhydride copolymer, olefinic copolymers such as ABS, polyester polyether elastomers, and one or more mixtures selected from elastomers such as polyester polyester elastomers. Polyester, liquid crystal polyester, polycarbonate, polyamide, polyphenylene sulfide, polyethylene, polypropylene, polystyrene, ABS, polyphenylene oxide, phenoxy resin, phenol resin, phenol-
One or a mixture of two or more selected from formaldehyde resins is preferable, more preferably polyester,
One or a mixture of two or more selected from polyamide, polyphenylene sulfide, ABS, polyphenylene oxide, phenoxy resin and phenol resin.

The amount of the phosphazene polymer used in the present invention is usually 1 to 1 with respect to 100 parts by weight of the thermoplastic resin.
The amount is 00 parts by weight, preferably 2 to 80 parts by weight, and more preferably 3 to 70 parts by weight.

The phosphazene polymer used in the present invention is preferably melt-kneaded at a temperature not lower than the melting point of the thermoplastic resin, but the phosphazene polymer used in the present invention can be added during the polymerization of the thermoplastic resin.

The flame retardancy of the flame-retardant resin composition of the present invention is further improved by adding a salt of cyanuric acid or isocyanuric acid. The salt of cyanuric acid or isocyanuric acid is an adduct of cyanuric acid or isocyanuric acid with a triazine-based compound, and usually has a composition of 1: 1 (molar ratio), and optionally 1: 2 (molar ratio). It is an adjunct that has. Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

The triazine compound is a compound represented by the following general formula (3).

[0046]

Embedded image (However, in the above formula, R1, R2, R3, and R4 are the same or different hydrogen alkyl groups, aralkyl groups, cycloalkyl groups, or -CONH2. Further, R is the same as -NR1R2 or -NR3R4 in the above formula. Group, or independently of them, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, -NH2, or -CO
It is a group selected from NH2. In the general formula (3), R1, R2, R3, and R4 are the same or different hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or -CONH2. Here, the aryl group has 6 to 15 carbon atoms,
The alkyl group is preferably one having 1 to 10 carbon atoms, the aralkyl group is preferably one having 7 to 16 carbon atoms, and the cycloalkyl group is preferably one having 4 to 15 carbon atoms. R is the same group as -NR1R2 or -NR3R4 in the above formula, or independently of them, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, -NH2, or -CONH.
A group selected from 2, wherein the aryl group has 6 to 15 carbon atoms and the alkyl group has 1 to 1 carbon atoms.
Preferred are those having 0, aralkyl groups having 7 to 16 carbon atoms, and cycloalkyl groups having 4 to 15 carbon atoms.

Specific examples of R1, R2, R3 and R4 include hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β-naphthyl group, methyl group, ethyl group, n-propyl group and isopropyl group. , N-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, 4-methyl- Examples thereof include a 1-cyclohexyl group and an amide group, and among them, hydrogen, a phenyl group, a methyl group, a hydroxymethyl group, a methoxymethyl group, a benzyl group and an amide group are preferable.

A specific example of R is an amino group,
Amide group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, mono (hydroxymethyl) amino group, di (hydroxymethyl) amino group, mono (methoxymethyl) amino group, di (methoxymethyl) amino group, Phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, among which hydrogen, an amino group, an amide group, a methyl group, a mono (hydroxymethyl) amino group, a di (hydroxymethyl) amino group, and a mono (methoxymethyl) group An amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferred.

Of the salts of the compound represented by the general formula (3) with cyanuric acid or isocyanuric acid, particularly preferred examples are melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine and tri (hydroxy). Methyl) melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,
Salts of 3,5-triazine are mentioned, and salts of melamine, benzoguanamine and acetoguanamine are particularly preferable.

The salt of the compound represented by the general formula (3) with cyanuric acid or isocyanuric acid is prepared by forming a mixture of the compound represented by the general formula (3) with cyanuric acid or isocyanuric acid into a water slurry. It is a powder obtained by mixing and forming both salts into fine particles, and filtering and drying this slurry, which is different from a simple mixture. This salt does not need to be completely pure, and may be a slightly unreacted compound of formula (3) or cyanuric acid,
Isocyanuric acid may remain. The form of this salt is not particularly limited, but it is preferable to use the one obtained as a powder as fine as possible from the viewpoint of mechanical strength and surface property of the molded article obtained from the composition of the present invention. It is particularly preferable that the average particle size before blending with the resin is 100 μm. If the dispersibility of the salt is poor,
A dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

In the present invention, a salt consisting of such a triazine compound and cyanuric acid or isocyanuric acid can be added as necessary. In this case, the amount of the salt used is based on the thermoplastic resin. 1 to 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to
70 parts by weight. If the amount of the salt used is less than 1 part by weight, the flame retardancy-improving effect is not recognized, and if it exceeds 100 parts by weight, the mechanical properties and surface appearance of the molded product are impaired, which is not preferable.

Further, the flame retardancy of the resin composition of the present invention can be further improved by adding a non-halogen flame retardant.

As such a non-halogen flame retardant,
There is no particular limitation as long as it is a flame retardant containing no halogen, but a flame retardant containing phosphorus is preferable, and specifically, those represented by the following general formulas (4) and (5) can be preferably mentioned.

[0054]

[Chemical 6] (However, the above formulas R5, R6, R7, R8, R9, R1
0, R11, R12, and R13 represent the same or different hydrogen atom or a C1-C5 alkyl group. A
r1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar
7 represents the same or different phenyl group or a phenyl group substituted with a halogen-free organic residue. Y is a direct bond, O, S, SO2, C (CH3) 2,
It represents CH2 or CHPh, and Ph represents a phenyl group. Further, n represents the number average degree of polymerization, and n is 0.5 or more.
Further, k and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. ) First, the structure of the flame retardant represented by the formula (4) will be described. In the formula (4), k and m are each 0 or more and 2
The following integers and k + m are integers of 0 or more and 2 or less, preferably k and m are integers of 0 or more and 1 or less, particularly preferably k and m are 1 respectively.

The number average degree of polymerization n is 0.5 or more.
Here, the number average degree of polymerization n is GPC (Gel Permeation Chrom
It is a value measured by atography and polystyrene conversion.

Among the compounds having a repeating unit structure represented by the above formula (4), it is difficult to accurately measure the number average molecular weight of the unit structure of each branched portion of the compounds having a branched structure. Therefore, the number average degree of polymerization n calculated from the number average molecular weight obtained by GPC measurement of the branched compound is divided by the number of branches (3-km), and the number average degree of polymerization n is 0.5 or more. .

In the formula (4), R5 to R13 represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and tert.
-Butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group and the like, but hydrogen,
A methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar1, Ar2, Ar3 and Ar4 represent the same or different phenyl groups or a phenyl group substituted with a halogen-free organic residue. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group, and a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable. Especially, a phenyl group, a tolyl group and a xylyl group are preferable.

Y is a direct bond, O, S, SO2, C
(CH3) 2, CH2, and CHPh are represented, and Ph represents a phenyl group.

The flame retardant represented by the above formula (4) is generally produced according to the following chemical formula (6). In this case, a low molecular weight phosphate such as triaryl phosphate may be mixed as a by-product. In that case, there is no particular problem as long as the number average degree of polymerization of the entire phosphate mixture is not less than 0.5.

[0061]

Embedded image Next, the flame retardant represented by the formula (5) will be described. In the above formula (5), Ar5, Ar6, and Ar7 represent the same or different phenyl groups or phenyl groups substituted with a halogen-free organic residue. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group, and a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable. Especially, a phenyl group, a tolyl group and a xylyl group are preferable.

The flame retardant represented by the above formula (5) can be generally produced according to the following chemical formula (7).

[0063]

Embedded image In the present invention, such a non-halogen flame retardant can be added if necessary, but the addition amount is usually 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
Parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to 70 parts by weight.

When the resin composition of the present invention is further added with a fluorine-based resin, the drop (drip) of droplets during combustion is suppressed. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / (Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

In the present invention, a fluororesin can be added if necessary, but the addition amount in this case is usually 0.01 to 10 per 100 parts by weight of the thermoplastic resin from the viewpoint of moldability. Parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

It was also found that the flame-retardant resin composition of the present invention, when used in combination with a hindered phenol-based stabilizer, maintains extremely good heat resistance even when exposed to high temperatures for a long period of time. Examples of such stabilizers include triethylene glycol-bis [3- (3-t-butyl-5)
-Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

In the present invention, such a hindered phenol-based stabilizer can be added if necessary, and the amount of the hindered phenol-based stabilizer added is usually 100 parts by weight of the thermoplastic resin. Against 0.01-3
The amount is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight.

Further, the resin composition of the present invention has periodic tables II to V.
Addition of a metal oxide, a metal hydroxide or a hydrate of a metal hydroxide having a group metal as a central atom can improve flame retardancy. As such a compound, specifically, aluminum hydroxide, aluminum hydroxide hydrate, magnesium hydroxide, magnesium hydroxide hydrate,
Examples thereof include zinc hydroxide, zinc hydroxide hydrate, boric acid, antimony oxide, zinc tin hydroxide, zinc tin hydroxide hydrate, zinc tin oxide, hydrotalcite and dawsonite.

The amount of the hydrated metal oxide, metal hydroxide or metal hydroxide added is usually 1 to 100 parts by weight, preferably 2 parts by weight, relative to 100 parts by weight of the thermoplastic resin.
The amount is from 80 to 80 parts by weight, more preferably from 3 to 70 parts by weight.

With respect to the resin composition of the present invention, phosphorus-based or sulfur-based antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, and dyes, etc., within the range not impairing the object of the present invention. One or more conventional additives such as colorants including pigments can be added.

Although not particularly required, strength, rigidity, heat resistance, etc. can be significantly improved by adding a fibrous and / or granular filler to the composition of the present invention. .

Specific examples of such a filler include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whiskers, wallastonite, glass flakes, glass beads, talc, mica, clay,
Examples thereof include calcium carbonate, barium sulfate, titanium oxide and aluminum oxide, and among them, chopped strand type glass fiber is preferably used. The addition amount of these is 5 to 1 with respect to 100 parts by weight of the thermoplastic resin.
It is preferably 40 parts by weight, particularly preferably 5 to 100 parts by weight.

The flame-retardant resin composition of the present invention is usually produced by a known method. For example, a method in which a thermoplastic resin, a Hoffphazene polymer, a triazine compound and a salt of cyanuric acid or isocyanuric acid and other necessary additives are melt-mixed in an extruder, or particles are uniformly mechanically mixed. Then, a method of molding at the same time as mixing with an injection molding machine can be mentioned.

The flame-retardant resin composition of the present invention can be molded by a generally known method such as injection molding, extrusion molding, blow molding and compression molding. Case member, transformer member,
It can be used for various purposes such as electric / electronic device parts such as coil bobbins, automobile parts, machine parts, and building materials.

[0075]

The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

(1) Solvent resistance evaluation of polyphosphazene 1 g of the synthesized polyphosphazene was made into 100 ml of a solution of water and methanol and stirred at 20 ° C. for 6 hours. The solution was filtered, the insoluble portion was removed, the solution was recovered, dried under reduced pressure, and the weight (w) of the phosphazene polymer dissolved in water and methanol was measured. The solubility of polyphosphazene was calculated from w / 1 × 100.

(2) Elution test of flame retardant 100 g of the resin composition was placed in a flask to prepare 100 ml of a water and methanol solution. After stirring at 20 ° C. for 6 hours, the solution was filtered and the solution was recovered. The solvent was removed from this solution at 100 ° C. under vacuum, the dissolved phosphazene polymer was recovered, and the weight (w1) was measured. The amount of phosphazene polymer in the resin composition was calculated from 100 g × phosphazene compounding amount (parts by weight) / 100 (w0), elution rate =
w1 / w0 × 100 was calculated.

(3) LOI (Limited Oxygen Concentration Index) A 150 mm × 6 mm × 1 mm strip-shaped test piece was prepared from the pellet, and the LOI was measured according to ASTM D-2863. The larger the LOI, the higher the flame retardancy.

(4) Flame Retardancy A 127 mm × 12.7 mm × 0.8 mm strip-shaped test piece was prepared from the pellets, and the flame retardancy was evaluated according to the evaluation standard defined in UL94.

The flame retardancy level is V-0>V-1>V-2>
It decreases in the order of HB.

(4) Thermal decomposition start temperature (Td) Using TGA (thermogravimetric analysis), a sample amount of 10 mg,
Under a nitrogen atmosphere, the temperature range of 100 to 850 ° C. is 20 ° C. /
The temperature was raised in minutes, and the temperature at which the weight loss started was defined as Td.

(5) Color tone of resin composition The dumbbell of the molded product was visually observed, and when badly colored, it was marked with X, when slightly colored, it was marked with Δ, and when it was not colored, it was marked with ◯.

Reference Example 1 Preparation of Phosphazene Polymer 350 g of phosphorus oxychloride was made into a solution of 500 ml of kerosene,
The aqueous ammonia solution was boiled to generate ammonia gas corresponding to 3 times mol of phosphorus oxychloride, and the ammonia gas was reacted with the phosphorus oxychloride solution through a trap filled with anhydrous KOH. During this period, the polymerization temperature was kept in the temperature range of 20 to 50 ° C. Predetermined amount of ammonia gas 3
After the addition over time, the reaction solution was heated to 150 ° C. and reacted for 2 hours. After 2 hours, the temperature was further raised to 200 ° C. and the reaction was carried out for 3 hours. The white precipitate was dropped in water, stirred for a while, and dried under reduced pressure at 100 ° C. and a reduced pressure degree of 10 mmHg. The dried white powder is further heated at 250 ° C and 1.0 mmH.
The mixture was allowed to react for 6 hours under reduced pressure of g to be stabilized to obtain a phosphazene polymer (A-1). Yield 75%. The temperature at 200 ° C. and 10% by weight reduction in a nitrogen atmosphere was 270 ° C. A-1 (1 g) in 100 ml of water, 20 ° C
The solubility was 1.5% by weight. The solubility in methanol at 20 ° C was 0.1% by weight. From the above results, it can be seen that a phosphazene polymer excellent in thermal stability and solvent resistance was obtained.

Reference Example 2 Manufacture of Phosphazene Polymer 350 g of phosphorus oxychloride was made into a solution of 500 ml of toluene, and ammonia gas in an amount 3 times that of phosphorus oxychloride was reacted with the phosphorus oxychloride solution through a trap filled with anhydrous KOH. It was The reaction temperature was kept in the temperature range of 50 to 80 ° C. After adding a predetermined amount of ammonia gas over 2 hours, the reaction solution was heated to 200 ° C. and reacted for 3 hours while distilling off the solvent toluene. Further, the degree of pressure reduction is 0.
It heated at 5 mmHg and 300 degreeC, and obtained the phosphazene polymer (A-2). Yield 80%. The temperature at which the weight was reduced by 10% by weight under a nitrogen atmosphere at 200 ° C was 310 ° C. The solubility of A-2 in 100 ml of water at 20 ° C was 2.1% by weight. From the above results, it can be seen that a phosphazene polymer excellent in thermal stability and solvent resistance was obtained.

Reference Example 3 Preparation of Phosphazene Polymer A phosphazene polymer was synthesized according to the method described in US Pat. No. 2,642,405.

350 g of phosphorus oxychloride, 500 ml of kerosene
Solution, and 5 times mol of ammonia gas of phosphorus oxychloride was reacted with the phosphorus oxychloride solution through a trap filled with anhydrous KOH. The reaction temperature was kept in the temperature range of 20 to 80 ° C. After adding a predetermined amount of ammonia, the reaction solution was heated to 200 ° C. and heated for 2 hours. The reaction solution was cooled, the white precipitate was collected by filtration, and the kerosene was removed by evaporation. Further, it was washed with a large amount of water and dried under reduced pressure to obtain a phosphazene polymer (B-1). 55% yield. The temperature at which the amount was reduced by 10% by weight under a nitrogen atmosphere was 190 ° C. A-1 (1g) water 10
The solubility at 20 ° C. in 0 ml was 90.0% by weight, and the solubility in methanol was 91.0% by weight. From the above results, it can be seen that the phosphazene polymer obtained by the method described in US2642405 has low thermal stability and low polymer yield, and further the solvent resistance of the phosphazene polymer is extremely poor.

The abbreviations, structures and number average degrees of polymerization of the non-halogen flame retardants (D) used in the examples and comparative examples are shown below. The following number average degree of polymerization n is a value measured using GPC under the following conditions.

Apparatus: Waters, column: TSK-G
2500H / TSK-G4000H Solvent: NMP (0.02N lithium chloride), Flow rate:
0.5 mL / min, detection: UV (260 nm)

Embedded image

When the cyanuric acid salt used in this example was observed with an electron microscope, the average particle size (average value of 100 solids) was smaller than 100 μm in all cases.

Examples 1 to 16 As the thermoplastic resin, PBT, PET, PC, ABS,
PC // ABS (80 // 20), Nylon 6 and Nylon 66 were used, and the phosphazene polymers (A-1, A-) of the present invention produced in Reference Examples 1 to 4 and having excellent thermal stability and water resistance were manufactured.
2), a salt of cyanuric acid or isocyanuric acid, and a non-halogen flame retardant other than the phosphazene polymer and other additives were mixed and melt-kneaded at a resin temperature of 260 ° C. using a 10 mmΦ single-screw extruder.

After drying the obtained pellets, a tensile test piece specified in ASTM D-638 was prepared by injection molding (mold temperature: 80 ° C.). Further, press molding was carried out to prepare a sample for LOI measurement, a sample for flame retardancy evaluation based on UL94, and a sample for elution test of a flame retardant and a coloring test. The compounding recipe is shown in Table 1. A series of evaluation results are shown in Table 2.

[0092]

[Table 1]

[0093]

[Table 2]

From the above results, by blending the phosphazene polymer of the present invention with a thermoplastic resin,
It can be seen that a resin composition excellent in thermal stability and water resistance and free from coloring can be obtained. The same applies when GF is added as a filler. It is also found that flame retardancy is improved by further adding a salt of a triazine compound and cyanuric acid or isocyanuric acid, a non-halogen flame retardant, a fluororesin or a metal hydroxide as an additive. It is also understood that the thermal stability is improved by adding the hindered phenol stabilizer.

Comparative Examples 1 to 10 As phosphazene polymers, red phosphorus (phosphorus chemistry was used instead of the phosphazene polymers (B-1) and phosphazene polymers having poor thermal stability and water resistance other than the phosphazene polymer of the present invention. Industry name, Novaret 12
0) and polyphosphoric acid amide (Sumitomo Chemical Co., Ltd.)
Manufactured by Sumisafe PM) and mixed with a salt of cyanuric acid or isocyanuric acid, a non-halogen flame retardant other than the phosphazene polymer, and other additives.
Melt kneading was carried out at a resin temperature of 260 ° C. using a 0 mmΦ single screw extruder.

After drying the obtained pellets, a tensile test piece specified in ASTMD-638 was prepared by injection molding (mold temperature: 80 ° C.). Further, press molding was carried out to prepare a sample for LOI measurement, a sample for flame retardancy evaluation based on UL94, and a sample for elution test of a flame retardant and a coloring test. The compounding recipe is shown in Table 3. A series of results are shown in Table 4.

[0097]

[Table 3]

[0098]

[Table 4]

From the above results, it can be seen that when red phosphorus or polyphosphoric acid amide is blended, the flame retardancy is improved, but the thermal stability, solvent resistance and coloring are poor. Further, it is clear that even if a phosphazene polymer other than the present invention having poor thermal stability and solvent resistance is blended, thermal stability and solvent resistance are inferior.

[0100]

The flame retardant comprising a specific phosphazene polymer is superior in thermal stability to conventionally known phosphorus-based flame retardants such as red phosphorus, polyphosphoric acid amide, and known phosphazene polymers. Further, the resin composition in which a specific phosphazene polymer is blended with a thermoplastic resin, particularly the coloring of the resin composition and the elution of the flame retardant in an aqueous solution are extremely small, and the connector, the relay, the switch, the case member, the transformer member, It can be used as a flame-retardant resin composition suitable for electric / electronic device parts such as coil bobbins, automobile parts, machine parts, and building materials.

Claims (11)

[Claims] 1. A heating test in nitrogen (heating rate of 10 ° C./min), which is substantially composed of a repeating unit represented by the following general formula (1) and is 10% by weight.
A flame retardant comprising a phosphazene polymer having a temperature of 200 ° C. or more at the time of weight reduction and a solubility in water and methanol at 20 ° C. of 10% by weight or less. Embedded image 2. A heating test in nitrogen which is an index of the thermal decomposition temperature and consists essentially of a repeating unit represented by the following general formula (1) per 100 parts by weight of the thermoplastic resin (heating rate). 1 to 100 parts by weight of a phosphazene polymer having a temperature of 200 ° C. or more at 10% by weight reduction and a solubility in water and methanol of 10% by weight or less at 20 ° C. A flame-retardant resin composition that is made up of. Embedded image 3. The flame-retardant resin composition according to claim 2, further comprising 1 to 100 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid. 4. The flame-retardant resin composition according to claim 3, wherein the triazine compound is melamine. 5. The flame-retardant resin composition according to claim 2, further comprising 1 to 50 parts by weight of a non-halogen flame retardant. 6. The flame-retardant resin composition according to claim 5, wherein the halogen-free flame retardant is a flame retardant containing phosphorus. 7. The flame-retardant resin composition according to claim 2, further comprising 0.01 to 10 parts by weight of a fluororesin. 8. A hindered phenol-based stabilizer 0.01-.
The flame-retardant resin composition according to claim 2, further comprising 3 parts by weight. 9. The flame-retardant resin composition according to claim 2, further comprising 5 to 140 parts by weight of a filler. 10. A compound further comprising 1 to 100 parts by weight of a hydrate of a metal oxide, a metal hydroxide or a metal hydroxide having a group II to V metal of the periodic table as a central atom. Two
The flame-retardant resin composition according to the above. 11. The flame retardant according to claim 2, wherein the thermoplastic resin is one kind or a mixture of two or more kinds selected from polyester, polyethylene, polypropylene, ABS, polyamide, polycarbonate, phenoxy resin, polyphenylene sulfide and phenol resin. Resin composition.