JP2001200151A - Flame-retardant polycarbonate resin composition and molded bodies thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition that has a high degree of flame retardancy occurring no burn-melt dripping without adverse effect on the high transparency and the mechanical strengths that are intrinsically excellent properties of aromatic polycarbonate. SOLUTION: The objective aromatic polycarbonate resin composition is obtained by formulating (B) 0.1-40 pts.wt. of at least one phenoxyphosphazene selected from cyclic phenoxyphosphazenes, chain phenoxyphosphazenes and crosslinkable phenoxyphosphazenes and (C) 0.01-50 pts.wt. of at least one compound selected from organic alkali metal salts, organic alkaline earth metal salts and organopolysiloxanes to (A) 100 pts.wt. of an aromatic polycarbonate resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polycarbonate resin composition. More specifically, the present invention relates to a highly flame-retardant polycarbonate resin composition which does not show dripping phenomena upon burning without impairing the transparency and mechanical properties inherent to the aromatic polycarbonate resin.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are excellent in mechanical strength (particularly, impact resistance), electric characteristics, transparency, etc., and are used in various fields such as electric / electronic devices, automobiles / machines, and construction. Widely used in Among these fields of use, there are fields that require a high degree of flame retardancy, mainly in the fields of OA equipment and electric / electronic equipment.

[0003] Among various thermoplastic resins, aromatic polycarbonate resins have a high oxygen index and generally have self-extinguishing properties. However, in terms of safety in OA equipment, electric and electronic equipment fields and other various uses. In order to satisfy the requirements, it is required to further enhance the flame retardancy and to maintain the inherent transparency characteristic of the aromatic polycarbonate resin.

Heretofore, various methods of blending an organic halide or an organic or inorganic sulfonate have been known as a method for making an aromatic polycarbonate resin flame-retardant.

More specifically, for example, a method of blending decabromodiphenyl oxide with an aromatic polycarbonate resin (Japanese Patent Application Laid-Open No. 54-52152) discloses a method of blending 2,2-terminal-blocked aromatic halide resin with halogenated phenol. Bis (4-hydroxy-3,5-dibromophenyl) propane (= tetrabromobisphenol-A)
Method of blending an aromatic polycarbonate (Japanese Patent Publication Sho 47)
JP-A-41422), a method of adding an oligomer of tetrabromobisphenol-A to an aromatic polycarbonate resin (JP-B-47-24660, JP-B-47-422).
44537 and JP-A-55-25466) are known. However, these methods have drawbacks in that heat stability during molding is reduced due to the addition of a halogen compound, and that corrosive or toxic gas or smoke is generated during molding or combustion.

In general, when an organic halide is used in combination with an antimony oxide compound (for example, antimony trioxide, sodium antimonate, etc.), an antimony halide is generated at the time of combustion, thereby shielding the surface and inhibiting the continuation of combustion. It is known that the flame retardancy is improved, and this technology is widely applied ("Chemical Handbook, Applied Chemistry, Fifth Edition", edited by The Chemical Society of Japan, published by Maruzen Co., Ltd., (1995), I
I, page 423). However, even when an organic halide and an antimony oxide compound are used in combination, the addition of the halogen compound is still the same, and the thermal stability at the time of molding is reduced as described above. There is the drawback of producing corrosive or toxic gases and smoke during combustion.

A method of blending an aromatic polycarbonate resin with an alkali metal salt of perfluoroalkane sulfonate (Japanese Patent Publication No. 47-40445, Japanese Patent Publication No. Sho 5-40)
No. 4-32456), a method of blending a metal salt of an aromatic sulfonamide (Japanese Patent Publication No. 56-45945),
A method of blending a metal salt of an aliphatic ether sulfonic acid (JP-B-54-106562), a method of blending a metal salt of an aromatic sulfonic acid (JP-B-57-28424, JP-B-58-43099), Japanese Patent Publication No. 58-13
587), and a method of blending a sulfate metal salt of an alcohol (JP-A-54-68857, JP-A-55-27303). However, these methods do not provide a thin-walled (for example, about 1.5 mm thick) aromatic polycarbonate resin molded product having a high flame retardancy that does not exhibit dripping phenomenon during combustion. In order to obtain sufficient flame retardancy with these compounds, it is necessary to add a large amount to the resin, and it is unavoidable that the aromatic polycarbonate resin becomes transparent and impairs transparency, which is an excellent property of the aromatic polycarbonate resin.

A method for preventing dripping during combustion by mixing an aromatic polycarbonate with an organic alkali metal salt or an alkaline earth metal salt and further adding polytetrafluoroethylene (Japanese Patent Publication No. 60-38418). ) Is disclosed, but this technique has a disadvantage in that the transparency, which is an essential feature of aromatic polycarbonate, is impaired.

Further, organic phosphoric acid esters are also known compounds as flame retardants (JP-A-7-41653).
It is. Although this organic phosphate ester retains transparency even when added in a large amount to the aromatic polycarbonate resin in order to satisfy the flame retardancy, the resin is plasticized because a large amount of the organic phosphate ester is added. This tends to lower the heat distortion temperature and deteriorate mechanical properties such as impact resistance. On the other hand, there is known a method of further adding a polyfluoroalkane, for example, polytetrafluoroethylene, for the purpose of preventing dripping during combustion in order to effectively obtain flame retardancy by adding a small amount of an organic phosphate. (Special 5
9-36657, Japanese Patent Publication No. 6-45747). However, in this method, it is inevitable that the transparency of the aromatic polycarbonate is lost by the addition of polytetrafluoroethylene.

On the other hand, in order to improve the flame retardancy of the aromatic polycarbonate resin, a method of copolymerizing a polysiloxane with an aromatic polycarbonate or a method of adding a silicone resin is known. For example, in order to obtain a flame-retardant polycarbonate resin, a method of using an aromatic polycarbonate-organopolysiloxane copolymer or a mixture of an aromatic polycarbonate-organopolysiloxane copolymer and an aromatic polycarbonate resin (Japanese Patent Application Laid-Open No. Sho 63)
-289059, JP-A-1-210462 and JP-A-4-202465) are known.
However, the flame retardancy of the aromatic polycarbonate-organopolysiloxane copolymer alone is still insufficient, and a polycarbonate resin having excellent flame retardancy has not yet been obtained.

Further, in order to obtain a flame-retardant resin composition, a method of blending various silicone resins with an aromatic polycarbonate resin (Japanese Patent Publication No. 62-60421, Japanese Patent Publication No.
JP-A-3-31513, JP-B-3-48947, JP-A-6-128434, JP-B-7-78171, JP-A-7-33971, JP-A-10-139
964, JP-A-11-140294). However, the siloxane copolymer or a compound having a siloxane structure such as a silicone resin has a small flame-retarding effect, and an effective flame-retarding effect cannot be exhibited unless it is added in a large amount. In order to obtain sufficient flame retardancy, if the added amount is increased, the moldability of the resin composition, various physical properties such as the appearance and mechanical strength of the molded article must be significantly reduced, and a large amount of silicone resin is required. , It is unavoidable that the resin composition itself becomes expensive. In addition, the silicone resin has insufficient dispersibility and compatibility with the aromatic polycarbonate resin, and two components having different refractive indices are phase-separated in the molded product, resulting in low transparency, or opaque when the blending amount is large. There is also a problem that you can get only what you need.

[0012] Accordingly, there is a demand for the development of an inexpensive and highly flame-retardant technology that maintains the physical properties and optical transparency of an aromatic polycarbonate resin and can be used for a wide range of applications.

[0013]

DISCLOSURE OF THE INVENTION The present invention relates to a polycarbonate resin composition having a high degree of flame retardancy which does not show dripping phenomena during combustion without impairing the inherent transparency and mechanical properties of the aromatic polycarbonate resin. The task is to provide

[0014]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, (A) 100 parts by weight of an aromatic polycarbonate resin, (B) a cyclic phenoxyphosphazene compound, 0.1 to 40 parts by weight of at least one phenoxyphosphazene compound selected from a phenoxyphosphazene compound and a crosslinked phenoxyphosphazene compound, and (C) an organic alkali metal salt;
It has been found that a resin composition containing 0.01 to 50 parts by weight of at least one selected from an organic alkaline earth metal salt and an organopolysiloxane can be a desired flame-retardant polycarbonate resin composition. The present invention has been completed based on such findings.

That is, the present invention provides: (A) 100 parts by weight of an aromatic polycarbonate resin, 0.1 to 40 parts by weight of (B) at least one phenoxyphosphazene compound selected from a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound and a crosslinked phenoxyphosphazene compound; C) at least one selected from organic alkali metal salts, organic alkaline earth metal salts and organopolysiloxanes 0.01
A flame-retardant polycarbonate resin composition comprising up to 50 parts by weight. 2. The cyclic phenoxyphosphazene compound of the component (B) has the general formula (1)

[0016]

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Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. ] The flame-retardant polycarbonate resin composition according to the above item 1, which is a cyclic phenoxyphosphazene represented by the following formula: 3. The chain phenoxyphosphazene compound of the component (B) is represented by the general formula (2)

[0018]

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Wherein X ¹ represents a group —N ＝ P (OPh) ₃ or a group —N ＝ P (O) OPh, and Y ¹ represents a group —P (OPh) ₄
Or a group -P (O) (OPh) ₂ . n is 3 to 100
Indicates an integer of 00. Ph is the same as above. ] The flame-retardant polycarbonate resin composition according to the above item 1, which is a chain phenoxyphosphazene represented by the following formula: 4. The crosslinked phenoxyphosphazene compound of the component (B) has the general formula (1)

[0020]

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[Wherein m represents an integer of 3 to 25]. Ph represents a phenyl group. A phenoxyphosphazene represented by the general formula (2):

[0022]

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Wherein X ¹ represents a group —N ＝ P (OPh) ₃ or —N ＝ P (O) OPh, and Y ¹ represents a group —P (OPh) ₄
Or a group -P (O) (OPh) ₂ . n is 3 to 100
Indicates an integer of 00. Ph is the same as above. At least one phosphazene compound selected from the group consisting of linear phenoxyphosphazenes represented by the following formulas: o-phenylene group, m-phenylene group, p-phenylene group and general formula (3)

[0024]

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[Wherein Z is -C (CH ₃ ) _2- , -SO
_{It represents 2-} , -S- or -O-. a represents 0 or 1. A compound cross-linked by at least one type of cross-linking group selected from the group consisting of bisphenylene groups represented by the formula (a): Interposed between atoms, (b)
The phosphazene compound (1) having a phenyl group content of
And / or 50 based on the total number of all phenyl groups in (2).
The flame-retardant polycarbonate resin composition according to the above item 1, which is a crosslinked phenoxyphosphazene compound having a hydroxyl group content of not more than 99.9% and (c) having no free hydroxyl group in the molecule. 5. The organic alkali metal salt or organic alkaline earth metal salt of the component (C) is an alkali metal salt of an organic sulfonic acid, an alkali metal salt of an organic phosphate, an alkali metal salt of an organic carboxylic acid, or an alkaline earth metal of an organic sulfonic acid. At least one selected from a salt, an alkaline earth metal salt of an organic phosphate and an alkaline earth metal salt of an organic carboxylic acid.
2. The flame-retardant polycarbonate resin composition according to the above 1, which is a seed. 6. 2. The flame-retardant polycarbonate resin composition according to the above item 1, wherein the organopolysiloxane as the component (C) is a phenyl-containing siloxane compound. 7. A flame-retardant polycarbonate resin molded article obtainable by molding the flame-retardant polycarbonate resin composition according to 1, 2, 3, 4, 5, or 6.

According to the present invention, the aromatic polycarbonate resin does not exhibit dripping phenomena during combustion without impairing the inherent transparency and mechanical properties (eg, impact resistance, dimensional stability, heat stability, etc.). A polycarbonate resin composition having high flame retardancy is provided.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) As the aromatic polycarbonate resin of the component (A) used in the present invention, an aromatic dihydroxy compound or a small amount of a polyhydroxy compound is reacted with a carbonyl halide or a carbonic acid diester. Obtained by
It is a thermoplastic aromatic polycarbonate polymer or copolymer which may be branched.

As the aromatic dihydroxy compound, conventionally known compounds can be widely used. Representative examples of aromatic dihydroxy compounds include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A),
2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Screw (4
-Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-t-butyl-4- Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-
Hydroxyphenyl) propane, 2,2-bis (3,5
-Dichloro-4-hydroxyphenyl) propane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl-1-phenylethane, bis ( Bis (hydroxyaryl) alkanes exemplified by 4-hydroxyphenyl) diphenylmethane; 1,1-bis (4
Bis (hydroxyaryl) cycloalkanes exemplified by -hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like;
4,4′-dihydroxydiphenyl ether, 4,4 ′
Dihydroxy diaryl ethers exemplified by -dihydroxy-3,3'-dimethyldiphenyl ether;
4,4′-dihydroxydiphenyl sulfide, 4,
Dihydroxydiaryl sulfides exemplified by 4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; etc .; exemplified by 4,4'-dihydroxydiphenyl sulphoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulphoxide and the like Dihydroxydiarylsulfoxides; dihydroxydiarylsulfones exemplified by 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; hydroquinone, resorcinol;
4,4'-dihydroxydiphenyl and the like.

In the present invention, these aromatic dihydroxy compounds may be used alone or as a mixture of two or more. Among these aromatic dihydroxy compounds, bis (4
-Hydroxyphenyl) alkanes, particularly 2,2-bis (4-hydroxyphenyl) propane, are preferably used.

In the present invention, the polyhydroxy compound is used in an amount of 0.0
A branched polycarbonate may be used in combination in the range of 1 to 3 mol% as a branching agent. As the polyhydroxy compound, conventionally known compounds can be widely used, for example, phloroglysin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -3-heptene, 4,6
-Dimethyl-2,4,6-tri (4-hydroxyphenyl) -2-heptene, 1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol,
α, α ', α "-tri (4-hydroxyphenyl)-
Examples include polyhydroxy compounds exemplified by 1,3,5-triisopropylbenzene and the like.

As the carbonyl halide or carbonic acid diester, conventionally known ones can be widely used, and specific examples include phosgene, diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The viscosity average molecular weight of the aromatic polycarbonate resin calculated from the viscosity of the methylene chloride solution at 25 ° C. is generally 10,000 to 100,000, preferably 15,000 to 6
It is 0000.

In the present invention, when producing an aromatic polycarbonate resin having such a viscosity average molecular weight, an appropriate molecular weight regulator, a catalyst for accelerating the reaction, and the like can be added as necessary. For example, monovalent aromatic hydroxy compounds suitable for adjusting the molecular weight include
Specifically, phenol, m-methylphenol, p
-Methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol,
Examples include alkyl-substituted products such as p-tert-octylphenol, p-cumylphenol and p-long-chain alkyl-substituted phenols, and halogen-substituted products such as p-bromophenol.

The aromatic polycarbonate resin of the component (A) used in the present invention may be used alone or as a mixture of two or more. Component (B) The phenoxyphosphazene compound (B) used as the flame retardant in the present invention is at least one selected from a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound and a crosslinked phenoxyphosphazene compound. As such a phenoxyphosphazene compound, conventionally known compounds can be widely used.

Examples of the cyclic phenoxyphosphazene compound include, for example, the cyclic phenoxyphosphazene compound represented by the above general formula (1).

Examples of the chain phenoxyphosphazene compound include, for example, the chain phenoxyphosphazene compound represented by the above general formula (2).

As the crosslinked phenoxyphosphazene compound, for example, at least one phosphazene compound selected from the group consisting of a cyclic phenoxyphosphazene represented by the general formula (1) and a chain phenoxyphosphazene represented by the general formula (2) Is a compound cross-linked by at least one cross-linking group selected from the group consisting of an o-phenylene group, an m-phenylene group, a p-phenylene group, and a bisphenylene group represented by the general formula (3). (A) the cross-linking group is interposed between the two oxygen atoms from which the phenyl group of the phosphazene compound is eliminated, and (b) the content of the phenyl group is in the phosphazene compound (1) and / or (2). Of 50 to 99. based on the total number of all phenyl groups.
And 9%, and (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule.

Among the phenoxyphosphazene compounds of the component (B), crosslinked phenoxyphosphazene compounds are preferred.

In the present invention, "having no free hydroxyl group in the molecule" means that it is described in the Analytical Chemistry Handbook (Revision 3).
Edition, edited by the Japan Society for Analytical Chemistry, Maruzen, 1981) No. 3
When quantified according to the acetylation method using acetic anhydride and pyridine described on page 53, it means that the amount of free hydroxyl groups is below the detection limit. Here, the detection limit is a detection limit as a hydroxyl equivalent per 1 g of a sample (crosslinked phenoxyphosphazene compound of the present invention), and more specifically, 1 × 10 ⁻⁶ hydroxyl equivalent / g or less.

When the crosslinked phenoxyphosphazene compound of the present invention is analyzed by the above-mentioned acetylation method, the amount of residual hydroxyl groups of the starting phenol is also added. However, since the starting phenol can be quantified by high performance liquid chromatography, the crosslinked phenoxy Only free hydroxyl groups in the phosphazene compound can be determined.

The cyclic phenoxyphosphazene compound and the chain phenoxyphosphazene compound used in the present invention are known compounds.

The crosslinked phenoxyphosphazene compound of the present invention is also a known compound, for example, of the general formula (4)

[0043]

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Wherein m is the same as above. And the general formula (5)

[0045]

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[Wherein X ² is a group -N = PCl ₃ or a group -N =
Represents P (O) Cl, and Y ² represents a group —PCl ₄ or a group —P
(O) Cl ₂ is shown. n is the same as above. At least one dichlorophosphazene compound selected from the group consisting of linear dichlorophosphazenes represented by the general formula (6):

[0047]

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[Wherein M represents an alkali metal. An alkali metal phenolate represented by the general formula (7):

[0049]

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[Wherein M is as defined above. An alkali metal diphenolate represented by the general formula (8):

[0051]

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Wherein Z, a and M are as defined above. A mixture with at least one diphenolate selected from the group consisting of alkali metal diphenolates represented by the following formula (first step), and further reacting the obtained compound with the alkali metal phenolate (second step). It is manufactured by

In the above production method, the dichlorophosphazene compounds represented by the general formulas (4) and (5) used as one of the raw materials are described in, for example,
87427, JP-B-58-19604, JP-B-61-1363, JP-B-62-20124, H, R, Allcock, "Phosphor.
us-Nitrogen Compounds ", Ac
ademic Press, (1972), JE.Ma.
rk, HR Allcock, R. West, "In
organic Polymers "Prentice
-Hall International, Inc.,
(1992) and the like.

As an example, first, ammonium chloride and phosphorus pentachloride (or ammonium chloride, phosphorus trichloride and chlorine) are mixed in chlorobenzene or tetrachloroethane.
By reacting at about 120 to 130 ° C. and dehydrochlorinating, a dichlorophosphazene compound represented by the general formula (4) in which m is 3 to 25 or a general formula (5) in which n is 3 to 25 A dichlorophosphazene compound represented by the following formula can be produced. These dichlorophosphazene compounds (dichlorophosphazene oligomers) are usually obtained as a mixture.

The cyclic and chain-like dichlorophosphazene oligomer mixture thus obtained is subjected to distillation or recrystallization to form a cyclic compound such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene or decachlorocyclopentaphosphazene. A dichlorophosphazene compound represented by the general formula (5) in which n is 25 to 10,000 is produced by heating a dichlorophosphazene compound or hexachlorocyclotriphosphazene to 220 to 250 ° C. and performing ring-opening polymerization. be able to.

The dichlorophosphazene compound produced as described above may be used alone or in the form of a mixture of cyclic and chain-like dichlorophosphazene, or may be used separately.

As the alkali metal phenolate represented by the general formula (6), conventionally known alkali metal phenolates can be widely used, for example, sodium phenolate, potassium phenolate,
Lithium phenolate and the like can be mentioned. These alkali metal phenolates can be used alone or in combination of two or more.

In the alkali metal diphenolate represented by the general formula (7), two groups -OM (M is the same as above) may be in any of ortho, meta or para positional relationship. Specific examples of the alkali metal diphenolate include, for example, alkali metal salts such as resorcinol, hydroquinone, and catechol. Among these, sodium salts and lithium salts are preferred. As the alkali metal diphenolate, one type can be used alone, or two or more types can be used in combination.

Examples of the alkali metal diphenolate represented by the general formula (8) include 4,4'-isopropylidene diphenol (bisphenol-A) and 4,4'-
Sulfonyl diphenol (bisphenol-S), 4,
Examples thereof include alkali metal salts such as 4'-thiodiphenol, 4,4'-oxydiphenol, and 4,4'-diphenol. Among these, sodium salts and lithium salts are preferred. As the alkali metal diphenolate, one type can be used alone, or two or more types can be used in combination.

In the present invention, the alkali metal diphenolate represented by the general formula (7) and the alkali metal diphenolate represented by the general formula (8) may be used alone or in combination. You may.

In the first step of the production method of the present invention, the chlorine atoms in the dichlorophosphazene compound are not completely consumed by the reaction with the alkali metal phenolate and the alkali metal diphenolate, that is, the chlorine atoms in the dichlorophosphazene compound are not consumed. It is desirable to control the amount of the alkali metal phenolate and the alkali metal diphenolate so that is still remained by the reaction with the alkali metal phenolate and the alkali metal diphenolate. Thereby, both of the alkali metal diphenolate-
An OM group (M is as defined above) is attached to the phosphorus atom of the dichlorophosphazene compound. In the first step, the amount of the alkali metal phenolate and the alkali metal diphenolate to be used is usually about 0.05 to 0.9 equivalent, preferably 0.1 to 0.9, in terms of the total amount of both phenolates based on the chlorine amount of the dichlorophosphazene compound. It may be about 1 to 0.8 equivalent.

In the second step of the production method of the present invention, the alkali metal phenolate is used so that all the chlorine atoms and free hydroxyl groups in the compound produced in the first step are completely consumed by the reaction with the alkali metal phenolate. It is desirable to adjust the amount of used. In the present invention, the amount of the alkali metal phenolate used is usually about 1 to 1.5 equivalents, preferably about 1 to 1.2 equivalents, based on the chlorine amount of the dichlorophosphazene compound.

In the present invention, the ratio of the alkali metal phenolate (total amount used in the first step and the second step) to the alkali metal diphenolate (alkali metal diphenolate / alkali metal phenolate, molar ratio) is usually from 1/2000 to 1/2000. About 1/4, preferably 1/20 to 1 /
6 may be used.

The reactions of the first step and the second step are each usually carried out at a temperature of about room temperature to about 150 ° C., preferably about 80 to 140 ° C., and usually for about 1 to 12 hours, preferably about 3 to 12 hours.
It ends in about 7 hours. The reaction in the first step and the reaction in the second step are usually performed in an organic solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene. Will be

The crosslinked phenoxyphosphazene compound of the present invention produced by the above reaction is, for example, washed, filtered,
It can be easily isolated and purified from the reaction mixture according to a usual isolation method such as drying.

The decomposition temperature of the crosslinked phenoxyphosphazene compound of the present invention is in the range of 250 to 350 ° C.

The content ratio of the phenyl group in the crosslinked phenoxyphosphazene compound of the present invention is determined by the ratio of the total phenyl group in the cyclic phenoxyphosphazene of the general formula (1) and / or the linear phenoxyphosphazene of the general formula (2). 50 to 99.9% based on the total number, preferably 70 to 9
0%.

The terminal groups X ¹ and Y ¹ in the general formula (2) vary depending on reaction conditions and the like. When a mild reaction is carried out under normal reaction conditions, for example, in a non-aqueous system, X ¹ But-
N = P (OPh) ₃ , Y ¹ has a structure of —P (OPh) ₄ , and under severe reaction conditions such that moisture or an alkali metal hydroxide is present in the reaction system, or a severe reaction in which a transfer reaction occurs. When the reaction was carried out under the conditions, X ¹ was -N = P
(OPh) ₃ , Y ¹ is —P (OPh) ₄ , and X ¹
There -N = P (O) OPh, Y 1 is -P (O) (OPh) ₂
It is in a state where those having the structure of are mixed.

In the present invention, the compounding amount of the phenoxyphosphazene compound as the component (B) is as follows.
It is necessary to be in the range of 0.1 to 40 parts by weight with respect to 0 parts by weight. When the blending amount of the phenoxyphosphazene compound (B) is less than 0.1 part by weight, the flame retardant effect is not exhibited, and when it exceeds 40 parts by weight, the obtained aromatic polycarbonate resin molded article is not cured. Causes deterioration in mechanical properties. In the present invention, the compounding amount of the phenoxyphosphazene compound which is the component (B) is the same as the above (A)
The amount is preferably in the range of 0.3 to 20 parts by weight based on 100 parts by weight of the component.

In the present invention, the cyclic, chain-like and cross-linked phenoxyphosphazene compounds of component (B) do not contain halogens such as chlorine and bromine. It does not emit harmful gas or smoke to living organisms, and does not cause corrosion of the mold, deterioration or coloring of the resin during resin molding. In addition, the phenoxyphosphazene compound of the present invention does not lower the molding temperature of the resin, has low volatility, and does not cause problems such as blocking and bleeding (juicing) during kneading and dripping during burning. Absent.

Since the crosslinked phenoxyphosphazene compound of the present invention is a crosslinked phenoxyphosphazene compound having substantially no hydroxyl group at one end of the dihydroxy compound, the molecular weight of the aromatic polycarbonate resin is not reduced, and the impact resistance is not reduced. Mechanical properties such as heat resistance,
There is no decrease in the inherent properties of the resin such as moldability and transparency. (C) Component In the present invention, at least one selected from organic alkali metal salts, organic alkaline earth metal salts, and organopolysiloxanes is used as the component (C).

Various kinds of organic alkali metal salts and organic alkaline earth metal salts are known. In the present invention, an alkali metal salt or alkali of an organic acid or organic acid ester having at least one carbon atom is used. At least one selected from earth metal salts is used.

Here, the organic acid or the ester of the organic acid is
It is an organic sulfonic acid, an organic carboxylic acid, an organic phosphoric acid ester, or the like, and may be substituted with a halogen such as fluorine, chlorine, or bromine, and may be an oligomer or a polymer. Examples of the oligomer and polymer include polymers such as polystyrene and polymers and oligomers having a sulfonyl group, a carboxyl group, a phospho group and the like in the molecule of the oligomer.

The organic sulfonic acids include, for example, 1-propanesulfonic acid, 1-hexanesulfonic acid,
Aliphatic sulfonic acids such as (2-methoxyethoxy) -1-propanesulfonic acid, 1,1-difluoro-1-butanesulfonic acid, 1,1,2-trifluoro-4-methoxy-1-butanesulfonic acid, 1,1,2,3,3,3-
Hexafluoro-1-propanesulfonic acid, perfluoromethanesulfonic acid, perfluoroethanesulfonic acid,
Fluorinated alkanesulfonic acids such as perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid; benzenesulfonic acid;
p-iodobenzenesulfonic acid, naphthalene-2,6-
Disulfonic acid, naphthalenetrisulfonic acid, 2,5-dichlorobenzenesulfonic acid, 3,4-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, 4,4′-dibromodiphenyl-3-sulfonic acid, 2,3,4,5,6-pentachloro-β-styrenesulfonic acid, 4,4′-dichlorodiphenylsulfide-3-sulfonic acid, tetrachlorodiphenyletherdisulfonic acid, 4,4′-dichlorobenzophenone-3,
3'-disulfonic acid, 2,5-dichlorothiophene-3
-Sulfonic acid, diphenylsulfone-3-sulfonic acid,
Diphenylsulfone-3,3'-disulfonic acid, 2,
Dimethyl 4,6-trichloro-5-sulfoisophthalate, dichlorophenyl 2,4,5-trichlorobenzenesulfonate, and 4 '-[1,4,5,6,7,7'-
Hexachlorobicyclo- [2,2,1] -hept-5-
[Ene-endo-yl] benzenesulfonic acid and the like.

Examples of the organic carboxylic acid include hexane carboxylic acid, heptane carboxylic acid, octane carboxylic acid, perfluoromethane carboxylic acid, perfluoroethane carboxylic acid, perfluoropropane carboxylic acid, perfluorobutane carboxylic acid, perfluoromethyl Butanecarboxylic acid, perfluorohexanecarboxylic acid, perfluoroheptanecarboxylic acid, perfluorooctanecarboxylic acid and the like.

Examples of the organic phosphate include di (pt-butylphenyl) phosphate and di (p-butylphenyl) phosphate.
Cumylphenyl) phosphate, di (brominated phenyl) phosphate, and the like.

On the other hand, examples of the alkali metal include sodium, potassium, lithium, and cesium, and examples of the alkaline earth metal include magnesium, calcium, strontium, and barium.

Specific examples of the organic alkali metal salt and organic alkaline earth metal salt of the component (C) include alkali metal salts of organic sulfonic acids, alkali metal salts of organic phosphoric acid esters, and alkali metal salts of organic carboxylic acids. , Alkaline earth metal salts of organic sulfonic acids, alkaline earth metal salts of organic phosphoric acid esters, alkaline earth metal salts of organic carboxylic acids, especially organic sulfonic acids, organic phosphoric acid esters, sodium such as organic carboxylic acids, Potassium and cesium salts are preferred.

In the resin composition of the present invention, the organic alkali metal salt or alkaline earth metal salt of the component (C) may be used alone or in combination of two or more. The compounding amount of the organic alkali metal salt or alkaline earth metal salt as the component (C) is 0.01 to 50 parts by weight based on 100 parts by weight of the resin (A). If this amount is 50
If the amount is more than 10 parts by weight, the physical properties of the aromatic polycarbonate resin are impaired, and it is economically disadvantageous. Conversely, 0.0
When the amount is less than 1 part by weight, the flame retardancy of the resin composition or the molded article is reduced.

In the present invention, from the viewpoints of resin physical properties and economy, the preferred amount of the organic alkali metal salt or alkaline earth metal salt which is the component (C) is 0.1 to 100 parts by weight of the component (A). The range is from 0.5 to 20 parts by weight.

The organopolysiloxane of the component (C) used in the present invention includes, for example, a phenyl-containing siloxane compound. Examples of the phenyl-containing siloxane compound include phenyl-containing siloxane compounds such as poly (diphenyl) siloxane and poly (methylphenyl) siloxane (= methylphenylsilicon), and phenyl-containing siloxane-polycarbonate copolymers such as poly (diphenyl) A siloxane-polycarbonate copolymer, a poly (methylphenyl) siloxane-polycarbonate copolymer, a copolymer having a polycarbonate block derived from a phenyl-containing siloxane and an aromatic polycarbonate block, and the like are included. These copolymers are more specifically described in JP-A-63-2890.
No. 59, Japanese Unexamined Patent Application Publication No. Hei 1-210462, Japanese Unexamined Patent Application Publication No.
Those described in JP-A-202465 can be widely used.

The organopolysiloxane of the component (C) is
(A) 0.01 to 50 parts by weight based on 100 parts by weight of the component.
It is advisable to mix the parts by weight, preferably 0.05 to 20 parts by weight. When the amount of the organopolysiloxane is more than 50 parts by weight, the transparency of the aromatic polycarbonate resin is lost, and the properties of the resin are also deteriorated. Conversely, when the amount is less than 0.01 parts by weight, the flame retardancy of the resin composition or the molded article decreases.

In the present invention, as the component (C), an organic alkali metal salt or an organic alkaline earth metal salt may be used alone, an organopolysiloxane may be used alone, or a combination of these may be used. You may. Other components In addition to the components (A), (B), and (C), the resin composition of the present invention may contain known additives that are generally used for flame retardation.
The aromatic polycarbonate resin can be used in an appropriate combination within a range that does not impair the original transparency of the aromatic polycarbonate resin.

There are no particular restrictions on the additives for flame retardancy as long as they maintain the transparency of the aromatic polycarbonate resin, and conventionally known additives can be widely used. For example, fine particulate zinc oxide can be used. Metal oxides such as, tin oxide, iron oxide, molybdenum oxide, copper oxide and manganese dioxide; aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum hydroxide treated with oxalic acid and magnesium hydroxide treated with nickel compound, etc. Metal hydroxides of sodium carbonate, calcium carbonate, barium carbonate,
Examples include antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide and sodium antimonate. Organic chlorine or bromine compounds such as chlorinated paraffin, perchlorocyclopentadecane, tetrabromobisphenol-A, tetrabromobisphenol-A epoxy oligomer or polymer, bis (tribromophenoxy) ethane and bis (tetrabromophthalimino) ethane; Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, diisopropylphenyl phosphate, octyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate,
Cresyl diphenyl phosphate, xylyl diphenyl phosphate, tolyl dixylyl phosphate and (2
Phosphate esters such as -ethylhexyl) diphenyl phosphate; hydroxyl-containing phosphate esters, resorcinol bis (diphenyl) phosphate, hydroquinone bis
(Diphenyl) phosphate, bisphenol-A bis (diphenyl) phosphate, resorcinol bis (dixylyl) phosphate, hydroquinone bis (dixylyl) phosphate, bisphenol-A bis (ditolyl) phosphate, biphenol bis (dixylyl) phosphate and bisphenol-A bis (dixylyl) ) Phosphate oxide compounds such as phosphates; red phosphorus, halogen-containing phosphoric acid ester compounds, halogen-containing condensed phosphoric acid ester compounds, phosphonic acid ester compounds, phosphine oxide compounds such as triphenylphosphine oxide and tolylphosphine oxide; melamine; Melamine cyanurate, melamine phosphate, melam, melem, melon, succinoguanamine, guanidine sulfamate, ammonium sulfate Nitrogen-containing compounds such as monium, ammonium phosphate, ammonium polyphosphate and alkylamine phosphate; boron compounds such as zinc borate, barium metaborate, and ammonium borate; silicon compounds such as silica; Can be used.

These additives may be used alone or in combination of two or more.

The resin composition of the present invention may further contain, if necessary, various kinds and amounts of various resin additives, fillers, other synthetic resins and elastomers which do not inhibit the properties of the present resin composition. Can be added. Examples of various resin additives include, for example, ultraviolet absorbers, light stabilizers, antioxidants, light-blocking agents, metal deactivators, quenchers, heat stabilizers, lubricants, release agents, coloring agents, antistatic agents, Antioxidants, plasticizers, impact strength improvers, compatibilizers and the like can be mentioned.

Among the various resin additives, examples of the ultraviolet absorber include benzotriazoles, benzophenones, salicylates, oxalic anilides, diphenylcyanoacrylates, triazines and oligomers and polymers having these skeletons. UV absorbers,
An inorganic ultraviolet absorber composed of ultrafine particles can be used.

For example, benzotriazole-based ultraviolet absorbers include 2- [2′-hydroxy-5 ′-(hydroxymethyl) phenyl] -2H-benzotriazole,
2- [2'-hydroxy-5 '-(hydroxyethyl)
Phenyl] -2H-benzotriazole, 2- [2′-
Hydroxy-3′-methyl-5 ′-(hydroxyethyl) phenyl] -2H-benzotriazole, 2-
[2′-Hydroxy-3′-t-butyl-5 ′-(hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′
-(Hydroxyethyl) phenyl] -5-chloro-2H
-Benzotriazole, 2,2'-methylenebis [6-
(5-chloro-2H-benzotriazol-2-yl)
-4- (2-hydroxyethyl) phenol], 2,
2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylenebis [6- (5-chloro-
2H-benzotriazol-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylenebis [6- (2H-benzotriazol-2-yl)-
4- (2-hydroxypropyl) phenol], 2,
2'-methylenebis [6- (5-chloro-2H-benzotriazol-2-yl) -4- (2-hydroxypropyl) phenol], 2,2'-methylenebis [6-
(5-chloro-2H-benzotriazol-2-yl)
-4- (4-hydroxybutyl) phenol], 6-
(2H-benzotriazol-2-yl) -4- (2-
Hydroxyethyl) phenol] ether, 2,2'-
Bis [6- (2H-benzotriazol-2-yl)-
4- (2-hydroxyethyl) phenol] sulfone and the like.

As the triazine-based ultraviolet absorber, for example, 2- (2,4-dihydroxyphenyl) -4,6-diphenyl-s-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -s-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethoxyphenyl) -s-triazine, 2- (2-hydroxy-4-
(2-hydroxyethyl) phenyl) -4,6-bis (2-hydroxy-4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (2-hydroxyethyloxy) phenyl) -4, 6-bis (2-hydroxy-4-dimethylphenyl) -s-triazine, 2-
(2-hydroxy-4- (3-hydroxypropyloxy) phenyl) -4,6-bis (2-hydroxy-4-
Dimethylphenyl) -s-triazine and the like.

Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol and pentaerythrityltetrakis [3- (3 ',
5'-di-tert-butyl-4'-hydroxyphenyl) -propionate], octadecyl-3- (3 ',
5'-di-tert-butyl-4'-hydroxyphenyl) -propionate, 2,2'-methylenebis (4-
Methyl-6-tert-butylphenol), 2,2 '
-Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-
6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol),
2,4-bis- (normal-octylthio) -6
4 "-hydroxy-3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3', 5'-di-tert-
Butyl-4'-hydroxyphenyl) -propionate], N, N'-hexamethylenebis (3,5-di-t
tert-butyl-4-hydroxyhydrocinnamide), 3,9- {2- [3- (3-butyl-4-hydroxy-5-methylphenyl) propionyloxy]-
1,1-dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

Examples of the sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, Stearyl-
3,3'-thiodipropionate, pentaerythrityl
-Tetrakis (3-mercaptopropionate), pentaerythrityl-tetrakis (3-laurylthiopropionate), bis {2-methyl-4-} 3-normal
Alkyl (C12 or C14) thiopropionyloxy {-5-tert-butylphenyl} sulfide, 2-
Mercaptobenzimidazole, glycerol-3-stearylthiopropionate and the like can be mentioned.

Examples of the phosphorus-based antioxidant include tris (nonylphenyl) phosphite, triphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diphenylisodecylphosphite, and diphenylisooctyl. Phosphite, distearylpentaerythritol diphosphite, di (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-)
(Butylphenyl) -4,4-biphenylisphosphonite and the like.

Examples of light stabilizers include 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-5-methyl-).
2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p
-Phenylenebis (3,1-benzoxazin-4-one), polyalkylene naphthalate and the like.

Examples of the filler include mica, kaolin, talc, silica, clay, calcium carbonate, calcium sulfate, calcium silicate, glass beads, glass balloon, glass flake, glass fiber, alumina, titanium oxide, and fibrous titanium. Alkali metal silicate, fibrous transition metal borate, alkaline earth metal borate, zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, gypsum whisker, aluminum silicate whisker, calcium silicate whisker, silicon carbide whisker,
Examples include titanium carbide whiskers, silicon nitride whiskers, titanium nitride whiskers, carbon fibers, alumina fibers, alumina-silica fibers, zirconia fibers, quartz fibers, and metal fibers.

The various additives and fillers described above may be used alone or as a mixture of two or more.

Other synthetic resins and elastomers can be appropriately mixed and used within a range that does not impair the transparency when mixed with a polycarbonate resin. For example, polyesters composed of an aromatic dicarboxylic acid or a derivative thereof and a dihydric phenol or a derivative thereof can be used.

In the present invention, a compound capable of securing flame retardancy or transparency can be combined as another additive. For example, oxygen-containing oligomers or polymers that promote carbonization of the resin when the resin burns, such as polyethylene glycol and polyvinyl alcohol. Further, oxygen-containing compounds such as trimethylolethane, trimethylolbutane, propanetrithiol, and pentaerythritol, and ether derivatives or ester derivatives thereof, or oligomers or polymers having the oxygen-containing compound as a basic skeleton are preferable. These may be used alone or in combination of two or more.

The resin composition of the present invention can be prepared by blending the above-mentioned components (A), (B) and (C) with various additives used as necessary, and kneading them. it can. For compounding and kneading, a method usually used, for example, a ribbon blender, a Henschel mixer, a V-type blender, a Nauta mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, and a It can be performed by a method using an axial screw extruder or the like. In addition, the heating temperature at the time of kneading can be appropriately selected usually in the range of 240 to 300 ° C.

The flame-retardant polycarbonate resin composition thus obtained can be easily molded by various known molding methods, for example, methods such as extrusion molding, injection molding, compression molding, calender molding, and rotational molding. It can also be applied to blow molding, vacuum molding, gas injection molding, etc., and is suitable for use in housings and chassis of electronic and electrical products, OA equipment, etc., which require excellent flame retardancy, and as a material for various parts. can do.

The resin composition thus obtained can be used in electrical, electronic, communication, agricultural, forestry and fishery, mining,
It can be used in industrial fields such as construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, furniture, printing and musical instruments. For example, printers, personal computers, word processors, keyboards, PDAs (small information terminals),
Telephones, facsimile machines, copiers, ECR (electronic cash register), calculators, electronic organizers, electronic dictionaries, cards, holders, stationery and other office and OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, Home appliances such as game machines, irons, kotatsu, TVs, VTRs, video cameras, digital cameras, boomboxes, tape recorders, minidiscs,
It is used for applications such as AV equipment such as CD players, PDs, DVDs, speakers, and liquid crystal displays, electrical and electronic parts such as connectors, switches, cables, and watches, 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, wheel 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,
Automobiles, vehicles, ships, aircraft such as deck panels, covers, plywood, ceiling boards, partition boards, side walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, soundproofing boards, heat insulating boards, window materials, etc. And building materials, clothing, curtains, sheets, plywood, plywood, carpets, doormats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, ski equipment,
Applications for living, sports and leisure goods such as rackets, tents, musical instruments, and toys.

[0102]

EXAMPLES Hereinafter, the present invention will be further clarified with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the evaluation of the resin composition was performed by the following method.

Flame retardancy : polycarbonate resin (component (A)) previously dried at 110 ° C. for 10 hours;
The required amount of the component (B), the component (C) and other components are added and mixed, and a twin screw extruder (S1-KRC 25mm Kneader: Co., Ltd.)
The mixture was kneaded and pelletized at 270 ° C. cylinder temperature and 260 ° C. nozzle temperature using Kurimoto Iron Works.

The obtained pellet was dried at 110 ° C. for 10 hours, and then heated to a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. using an injection molding machine (MINIMAT-26 / 15B, manufactured by Sumitomo Heavy Industries, Ltd.). To form a 1/16 inch (approximately 1.6 mm) thick, 12.5 mm wide, 127 mm long compact,
-94V test method (Test for Flammability of Plastic
Materials for Parts in Devices and Appliances UL
94, Fourth Edition).

Average burning time : In the above-mentioned flame retardancy test, it was shown as the total number of seconds of framing after 10 times of flame contact, two times for each set of five test pieces.

Drip : In the flame retardancy test, five test pieces were brought into contact with the flame 10 times in total, and during the combustion test, the number of flaming grains (drip) that ignited cotton 30 cm below was measured.

HAZE : A test piece having a thickness of 3 mm, a width of 50 mm, and a length of 90 mm was molded in the same manner as in the case of the evaluation of flame retardancy described above, and H was measured in accordance with JIS K-7105-1981.
AZE METER (trade name: HAZE METER NDH 2000,
HAZE (%) was measured using Nippon Denshoku Industries Co., Ltd.) and used as an index of transparency.

Synthesis Example 1 Phenoxyphosphazene ([N
= P (-OPh) ₂ ] ₃ and [N = P (-OPh) ₂ ] ₄ , hereinafter abbreviated as "FR-1". Synthesis of H.) R. Allcock, "Phosphorus-
Nitrogen Compounds ", Acade
FR-1 was produced according to the method described in Mic Press, (1972), 151.

That is, 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) of a dichlorophosphazene oligomer (a mixture of 62% trimer and 38% tetramer) was added with toluene of sodium phenolate. After the solution was added under stirring, the mixture was reacted at 110 ° C. for 10 hours.
The residual chlorine content of the product was <0.01%, and it was confirmed that the product was the following compound.

[N = P (-OPh) ₂ ] _3,4 Synthesis Example 2 Synthesis of a phenoxyphosphazene compound having a crosslinked structure with paraphenylene (hereinafter abbreviated as “FR-2”) 1.1 mole (103. A mixture of 5 g) of phenol, 1.1 mol (44.0 g) of sodium hydroxide, 50 g of water and 500 ml of toluene was heated to reflux, and only water was removed from the system to prepare a toluene solution of sodium phenolate. .

In parallel with the above reaction, 0.15 mol (16.5 g) of hydroquinone was placed in a two-liter four-necked flask.
A mixture of 1.0 mol (94.1 g) of phenol, 1.3 mol (31.1 g) of lithium hydroxide, 52 g of water and 600 ml of toluene was heated and refluxed to remove only water out of the system. A toluene solution of lithium salt of hydroquinone and phenol was prepared. To this toluene solution was added dichlorophosphazene oligomer (trimer 72
%, Tetramer 15%, pentamer and hexamer 8%, heptamer 3
%, A mixture of octamer and 2%) 1.0 unit mol (1
580 g of a 20% chlorobenzene solution containing 15.9 g)
Was added dropwise at 30 ° C. or lower with stirring, and then reacted at 110 ° C. for 4 hours with stirring. Next, the toluene solution of sodium phenolate prepared above was added under stirring, and then 110 ° C.
For 8 hours.

After completion of the reaction, the reaction mixture was washed three times with 1 liter of a 3% aqueous sodium hydroxide solution and then three times with 1 liter of water, and the organic layer was concentrated under reduced pressure. The obtained product was concentrated to dryness at 80 ° C. and 266 Pa or lower to obtain 211 g of a white powder.

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained above is 0.01% or less, and the composition of the final product is determined from the phosphorus content and the CHN elemental analysis value.
[N = P (-Op-Ph-O-) _0.15 (-O-Ph)
_1.7 ].

The weight average molecular weight (Mw) was 1100 in terms of polystyrene (by GPC analysis), and TG / DT
A analysis did not show a clear melting point, and the decomposition onset temperature was 306.
° C, 5% weight loss temperature was 311 ° C.

Further, the residual hydroxy group was quantified by the acetylation method. As a result, the residual hydroxyl group was below the detection limit (hydroxy equivalent per 1 g of sample: 1 × 10 ⁻⁶ equivalent / g or less). Synthesis Example 3 Synthesis of phenoxyphosphazene compound (hereinafter abbreviated as “FR-3”) having a crosslinked structure with 2,2-bis (p-oxyphenyl) isopropylidene group 0.7 mol (65.9 g) of phenol and Toluene 50
0 ml was placed in a 1-liter four-necked flask, and while stirring, the internal liquid temperature was kept at 25 ° C.,
Gram atoms (14.9 g) were finely cut and charged.
After completion of the charging, stirring was continued at 77 to 113 ° C. for 8 hours until the sodium metal completely disappeared.

In parallel with the above reaction, bisphenol-A
0.25 mol (57.1 g), phenol 1.1 mol (103.5 g) and tetrahydrofuran (THF) 8
00 ml into a 3 liter four-necked flask, and with stirring,
While maintaining the internal liquid temperature at 25 ° C., 1.6 g atom (11.1 g) of metallic lithium was finely cut and charged. After completion of the charging, stirring was continued for 8 hours at 61 to 68 ° C. until the lithium metal completely disappeared. To this slurry solution, dichlorophosphazene oligomer (trimer 72%, tetramer 1
386 g of a 30% chlorobenzene solution containing 1.0 unit mol (115.9 g) containing 5%, pentamer and hexamer 8%, heptamer 3%, octamer or more 2%) was stirred under stirring. The solution was added dropwise over 1 hour while maintaining the internal liquid temperature at 20 ° C. or lower, and then reacted at 80 ° C. for 4 hours. Next, while stirring, the sodium phenolate solution separately prepared was added over 1 hour while maintaining the internal liquid temperature at 20 ° C., followed by a reaction at 80 ° C. for 10 hours.

After the completion of the reaction, the reaction mixture was concentrated to remove THF, and 1 liter of toluene was newly added. The toluene solution was washed three times with 1 liter of 2% NaOH and then three times with 1 liter of water, and the organic layer was concentrated under reduced pressure. The obtained product was concentrated and dried at 80 ° C. and 266 Pa or less to obtain 230 g of a white powder.

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained above was 0.01% or less, and the composition of the final product was determined from the phosphorus content and CHN elemental analysis.
[N = P (-O-Ph -C (CH 3) 2 -Ph-O-)
_0.25 (-O-Ph) _1.50 ].

The weight average molecular weight (Mw) was 1140 in terms of polystyrene (by GPC analysis), and TG / DT
A analysis showed no clear melting point and decomposition onset temperature was 310
° C, 5% weight loss temperature was 315 ° C.

The residual hydroxyl group was quantified by the acetylation method. As a result, the residual hydroxyl group was below the detection limit (hydroxyl equivalent per gram of sample: 1 × 10 ⁻⁶ equivalent / g or less). Synthesis Example 4 Synthesis of phenoxyphosphazene (hereinafter abbreviated as “FR-4”) having a crosslinked structure with 4,4-sulfonyldiphenylene (bisphenol-S residue) 0.4 mol of phenol (37.6 g) and tetrahydrofuran 500 ml of (THF) was placed in a 1-liter four-necked flask, and 0.45 g atom (9.2 g) of metallic sodium was finely cut and charged under stirring while maintaining the internal liquid temperature at 25 ° C. After completion of the charging, stirring was continued at 65 to 72 ° C. for 5 hours until the metallic sodium completely disappeared.

In parallel with the above reaction, 1.70 mol (160.0 g) of phenol and 0.05 mol (12.5 g) of bisphenol-S were added to T in a 1 liter four-necked flask.
Dissolved in 500 ml of HF, charged with 1.8 g atoms (41.4 g) of metallic sodium at 25 ° C. or lower, heated to 61 ° C. over 1 hour after completion of the charging, continued stirring at 61 ° C. to 68 ° C. for 6 hours, A sodium phenolate mixed solution was prepared. 1.0 unit mol of a dichlorophosphazene oligomer (a mixture of 72% trimer, 15% trimer, 8% pentamer and hexamer, 3% heptamer, 3% octamer and 2% octamer) (115.9 g) in a 20% chlorobenzene solution 58
After dropping 0 g under cooling and stirring at 25 ° C. or less, 71 to 7
The mixture was stirred and reacted at 3 ° C. for 5 hours. Next, after the sodium phenolate mixed solution prepared above was dropped, 71 to 73 ° C.
For 10 hours.

After completion of the reaction, the reaction mixture was concentrated, redissolved in 500 ml of chlorobenzene, washed 3 times with 5% aqueous NaOH, washed with 5% sulfuric acid, washed with 5% aqueous sodium bicarbonate, and washed 3 times with water. 220g of white solid
I got

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained above is 0.01% or less. From the phosphorus content and CHN elemental analysis, the composition of this product is almost [N = P (-O-Ph). _{-SO 2 -Ph-O-) 0.05 (} -
O-Ph) _1.90 ].

The weight average molecular weight (Mw) was 1070 in terms of polystyrene, the melting temperature (Tm) by TG / DTA analysis was 103 ° C., the decomposition starting temperature was 334 ° C., and the 5% weight loss temperature was 341 ° C.

Further, as a result of quantifying the residual hydroxy group by the acetylation method, the detection limit was obtained (the hydroxy equivalent per 1 g of sample: 1 × 10 ⁻⁶ equivalent / g or less).
It was below.

Example 1 Polycarbonate resin (trade name: Iupilon, S-20)
00F, viscosity average molecular weight: 22,900, 100 parts by weight, FR-12.5 parts by weight, and potassium perfluorobutanesulfonate (hereinafter abbreviated as "C-1") (Wako Pure Chemical Industries, Ltd.) Industrial Co., Ltd.)
After dry blending 0.2 parts by weight in advance, the mixture was supplied to a hopper of a twin-screw extruder having a cylinder temperature set at 270 ° C. and melt-extruded to obtain a pellet-shaped resin composition of the present invention.

Examples 2 to 4 Resin compositions of the present invention were obtained in the same manner as in Example 1 except that FR-1 in Example 1 was changed to FR-2, FR-3 or FR-4. .

Examples 5 to 8 C-1 in Example 1 was replaced by methylphenylsilicon (trade name: TSF-4300, manufactured by Toshiba Silicone Co., Ltd.)
(Hereinafter abbreviated as "C-2"), except that they were blended as shown in Table 1, and the resin compositions of the present invention were obtained in the same manner as in Example 1.

Examples 9 to 10 Same as Example 1 except that trimethylolethane (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter abbreviated as "D-1") was added to the formulations in Examples 1 and 5. Thus, the resin compositions of the present invention were obtained.

Comparative Examples 1 to 3 Resin compositions were obtained in the same manner as in Example 1 except that each compounding agent was changed as shown in Table 1.

Compounding amounts of component (B), component (C) and other components in Examples 1 to 10 and Comparative Examples 1 to 3 (compounding amount (parts by weight) relative to 100 parts by weight of component (A))
Are shown in Table 1 and the evaluation results are shown in Table 2.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

Industrial Applicability The flame-retardant polycarbonate resin composition of the present invention can prevent dripping at the time of burning without impairing the transparency and physical properties inherent to polycarbonate, and can exhibit high flame retardancy. Therefore, the flame-retardant polycarbonate resin composition of the present invention is suitably used as a material for various molded articles, for example, electric / electronic parts, OA equipment parts, automobile / machine parts, building materials and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83:04) C08L 83:04) (72) Inventor Hiroyuki Takase 463 Kagasuno, Kawauchi-cho, Tokushima-shi, Tokushima Otsuka F-term in Tokushima Research Laboratory (reference) 4F071 AA50 AA67 AA68 AC09 AC14 AC15 AE07 AH01 AH03 AH04 AH07 AH12 AH19 BB03 BB04 BB05 BB06 BC07 4J002 CG011 CP033 CQ012 EG027 EG030 FD057 FD010 GFD FD010 GFD

Claims (7)

[Claims] (A) Aromatic polycarbonate resin 10
0 parts by weight of (B) 0.1 to 40 parts by weight of at least one phenoxyphosphazene compound selected from a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound and a crosslinked phenoxyphosphazene compound, and (C) an organic alkali metal salt; At least one selected from organic alkaline earth metal salts and organopolysiloxanes;
A flame-retardant polycarbonate resin composition comprising 0.01 to 50 parts by weight of a seed. 2. The cyclic phenoxyphosphazene compound of the component (B) is represented by the general formula (1): [In the formula, m represents an integer of 3 to 25. Ph represents a phenyl group. The flame-retardant polycarbonate resin composition according to claim 1, which is a cyclic phenoxyphosphazene represented by the following formula: 3. The chain phenoxyphosphazene compound of the component (B) is represented by the general formula (2): [Wherein X ¹ is a group -N = P (OPh) ₃ or a group -N = P
(O) OPh, wherein Y ¹ is a group -P (OPh) ₄ or a group-
P (O) (OPh) ₂ is shown. n shows the integer of 3-10,000. Ph is the same as above. The flame-retardant polycarbonate resin composition according to claim 1, which is a chain phenoxyphosphazene represented by the following formula: 4. The crosslinked phenoxyphosphazene compound of the component (B) is represented by the general formula (1): [In the formula, m represents an integer of 3 to 25. Ph represents a phenyl group. A phenoxyphosphazene represented by the general formula (2): [Wherein X ¹ is a group -N = P (OPh) ₃ or a group -N = P
(O) OPh, wherein Y ¹ is a group -P (OPh) ₄ or a group-
P (O) (OPh) ₂ is shown. n shows the integer of 3-10,000. Ph is the same as above. At least one selected from the group consisting of linear phenoxyphosphazenes represented by
Kinds of phosphazene compounds include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a compound represented by the general formula (3). [Wherein Z is _{-C (CH 3) 2 -,} - SO 2 -, - shows S- or -O-. a represents 0 or 1. A compound crosslinked by at least one kind of crosslinking group selected from the group consisting of bisphenylene groups represented by the formula (a):
And (b) the phenyl group content is 50 to 99.9% based on the total number of all phenyl groups in the phosphazene compound (1) and / or (2).
The flame-retardant polycarbonate resin composition according to claim 1, which is (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule. 5. The organic alkali metal salt or organic alkaline earth metal salt of the component (C) is an alkali metal salt of an organic sulfonic acid, an alkali metal salt of an organic phosphate, an alkali metal salt of an organic carboxylic acid, or an organic sulfonic acid. The flame-retardant polycarbonate resin composition according to claim 1, which is at least one member selected from the group consisting of alkaline earth metal salts of organic phosphates, alkaline earth metal salts of organic phosphates, and alkaline earth metal salts of organic carboxylic acids. . 6. The flame-retardant polycarbonate resin composition according to claim 1, wherein the organopolysiloxane as the component (C) is a phenyl-containing siloxane compound. 7. A flame-retardant polycarbonate obtainable by molding the flame-retardant polycarbonate resin composition according to claim 1, claim 2, claim 3, claim 4, claim 5, or claim 6. Resin molding.