JP2001288352A - Flame-retarded polycarbonate composition and its molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate composition improved so that molded products therefrom are not contaminated, without being deteriorated in flame retardance and mechanical characteristics, and further having an excellent thermal stability, when molded. SOLUTION: This flame-retardant polycarbonate composition comprises 100 pts.wt. of a polycarbonate, 0.001-10 pts.wt. of a phosphoric acid phosphonium salt compound having a specified structure and, if required, 0.0001-5 pts.wt. of a phosphonic acid phosphonium salt having a specific structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant polycarbonate composition, and more particularly to a flame-retardant polycarbonate composition containing a specific phosphonium phosphate and a molded product thereof. In the present specification, “polycarbonate” may be referred to as “polycarbonate resin”. Further, the present invention relates to the polycarbonate composition and a molded product thereof which can be suitably used for applications in which dust of plastic parts such as lenses, films, sheets and the like easily adheres to dust. Still another object of the present invention relates to a flame-retardant polycarbonate composition having excellent transparency and hue stability, and a molded product thereof.

[0002]

2. Description of the Related Art Polycarbonate is excellent in optical properties, electrical properties, dimensional stability, mechanical properties such as impact resistance and breaking strength, heat resistance, transparency and the like. Therefore, it is widely used for a wide range of applications.
Above all, it is widely used for lenses, glasses, prisms, optical disks, sheets, films, etc., taking advantage of its transparency.

[0003] Optical applications such as lenses, glasses, prisms, and optical disks require excellent transparency and hue, retention stability during molding such as heat stability and hue stability, and also moldability and wet heat durability. Environmental stability such as performance is required.

[0004] Further, from the expansion of the range of use, development of polycarbonate having flame retardancy in addition to the inherent properties of polycarbonate is expected.

In the above-mentioned optical applications, when dust adheres, there is a serious problem that the essential function and performance of the molded product are lost. Since a defect causes a serious problem of a reduction in commercial value, development of a flame-retardant polycarbonate resin excellent in dust adhesion prevention property, that is, excellent in antistatic property in addition to flame retardancy is expected.

[0006] On the other hand, from the standpoint of molding processing, when molding a resin composition, particularly when molding processing is continuously performed for a long time, or during molding processing, the molding processing is interrupted and restarted. In the case, the problem of the thermal stability of the resin composition, especially the yellowing or the decrease in the molecular weight of the composition containing various flame retardants, or the problem of generating black foreign matter, etc., still remains unsolved. I have.

[0007]

DISCLOSURE OF THE INVENTION The present invention improves the stain resistance due to the adhesion of dust to molded articles without impairing the flame retardancy and mechanical properties, and also provides excellent thermal stability during molding. An object of the present invention is to provide a flame-retardant polycarbonate composition having the same. The present invention further provides a composition and a molded article having improved flame retardancy and dust adhesion without impairing the inherent transparency of polycarbonate, in addition to the above-mentioned problems.

[0008]

That is, the present invention is as follows. 1. The main repeating unit is a polycarbonate represented by the following general formula (1) and one of the polycarbonates
0.001 to 10 parts by weight per 00 parts by weight of a flame-retardant polycarbonate composition comprising at least one selected from the group consisting of phosphonium phosphate compounds having a specific structure represented by the following general formula (2).

[0009]

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(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, W is an alkylidene group or an alkylene group. , A cycloalkylidene group, a cycloalkylene group, a phenyl-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.)

[0011]

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(In the formula (2), R ₅ , R ₆ , R ₇ and R ₈ each independently represent an alkyl group, an aralkyl group or an aryl group having 1 to 10 carbon atoms and which may have a substituent. X and Y each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an ammonium base, a phosphonium base or an alkali metal.)

2. The above-mentioned 1 characterized in that it contains at least one selected from the group consisting of phosphonium phosphonate salts having a specific structure represented by the following general formula (3) in an amount of 0.0001 to 5 parts by weight per 100 parts by weight of the polycarbonate. The flame-retardant polycarbonate composition according to the above.

[0014]

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(In the formula (3), R ₄₁ -R ₄₄ is the same as R ₅ -R ₈₎
And Z ₃ is the same as X in the formula (2), and Z represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. )

3. The terminal group of the polycarbonate is substantially composed of an aryloxy group and a phenolic hydroxyl group, the phenolic hydroxyl group concentration is 50 mol% or less, and the melt viscosity stability of the polycarbonate is 0.5% or less. 3. The flame-retardant polycarbonate composition according to the above 1 or 2.

4. Polycarbonate, from an aromatic dihydroxy compound and a carbonic acid diester, at least one compound selected from the group consisting of basic nitrogen-containing compounds and basic phosphorus-containing compounds, and at least one kind selected from the group consisting of alkali metal compounds 4. The flame-retardant polycarbonate composition according to any one of the above items 1 to 3, which is subjected to melt polycondensation in the presence of a catalyst comprising a compound.

5. A molded article comprising the polycarbonate composition according to any one of the above items 1 to 4.

6. 6. The molded article according to the above item 5, wherein the molded article is a device exterior plastic part.

[7] FIG. 6. The molded product according to the above item 5, wherein the molded product is an optical disk substrate.

In one embodiment of the present invention, a group of phosphonium phosphates having a specific structure represented by the general formula (2) is added to 100 parts by weight of a polycarbonate mainly having a specific repeating structure represented by the general formula (1). Provided is a flame-retardant polycarbonate composition containing at least one compound selected from compounds in a proportion of 0.001 to 10 parts by weight.

[0022]

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[0023]

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(In the formula (1), R ₁ , R ₂ , R ₃ , R ₄
Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group; W represents an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, a phenyl-substituted alkylene group, an oxygen atom, a sulfur atom; An atom, a sulfoxide group, or a sulfone group. In the formula (2), R ₅ , R ₆ , R ₇ and R ₈ each independently represent an alkyl group, an aralkyl group or an aryl group having 1 to 10 carbon atoms and which may have a substituent. Represent. X and Y each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an ammonium base, a phosphonium base and an alkali metal. )

It is conventionally known that certain phosphoric ester compounds are used for improving the flame retardancy. In fact, although it is effective to some extent in improving the flame retardancy of a polycarbonate composition, the adhesion of dust to a molded product is reduced. It is known that prevention is often worsened.

On the other hand, the inventors of the present invention have reported that the phosphonium phosphate having the specific structure of the present invention improves the antistatic property and remarkably improves dust adhesion,
Even more surprisingly, they have found that flame retardancy can also be achieved without compromising transparency, and have reached the present invention.

With respect to ionic compounds such as sodium sulfonate which have been conventionally used for the purpose of preventing static electricity and preventing dust adhesion, it is considered that the heat stability of the polycarbonate composition and the transparency are deteriorated. It is surprising that the phosphonium phosphate of the present invention does not adversely affect the stability and transparency of the polycarbonate composition, unlike sodium sulfonate.

Furthermore, when the phosphonium phosphonate salt represented by the following general formula (3) is used in combination with the phosphonium phosphate salt, the flame retardancy is further improved without deteriorating the stability and transparency of the polycarbonate composition. Improving is an effect that may not be evident from conventional knowledge.

The polycarbonate used in the present invention is:
An aromatic dihydroxy compound represented by the general formula (4):

[0030]

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(R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, and W is an alkylidene group, an alkylene group or a cycloalkylidene group. , A cycloalkylene group, a phenyl group-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.) A carbonate bond-forming precursor is reacted by a solution method or a melting method.

Among the polycarbonates produced by the melt method, in the present invention, at least one selected from the group consisting of polycarbonates polycondensed in the presence of a transesterification catalyst, especially basic nitrogen-containing compounds and basic phosphorus-containing compounds. In the presence of a transesterification catalyst comprising a kind of compound and at least one kind of compound selected from the group consisting of alkali metal compounds, polycarbonate subjected to melt polycondensation is an object of the present invention, that is, the stability at the time of molding and processing. Is preferably used.

As the aromatic dihydroxy compound represented by the general formula (4), specifically, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1- Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-
Bis (4-hydroxyaryl) alkanes such as 3-methylphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 4,4′-dihydroxyphenyl-1,1′-m-diisopropylbenzene, 1,1
-Bis (4-hydroxyphenyl) cyclohexane, 1
-Methyl-1- (4-hydroxyphenyl) -4- (dimethyl-4-hydroxyphenyl) methyl-cyclohexane, 4- [1- [3- (4-hydroxyphenyl)-
4-methylcyclohexyl] -1-netylethyl] -phenol, 4,4 ′-[1-methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol, 4,4′-dihydroxy-3, Bis (hydroxyaryl) cycloalkanes such as 3'-dimethylphenyl-9,9-fluorene dihydroxyaryl ethers such as bis (4-hydroxyphenyl) ether; 4,4'-dihydroxydiphenyl sulfide; 4,4 ' -Dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethyldiphenyl sulfide; dihydroxy diaryl sulfosulfides such as 4,4'-dihydroxy diphenyl sulfoxide; 4,4'-dihydroxy diphenyl sulfone; and 4,4'-dihydroxy-3,3'- Dihydroxydiarylsulfones such as dimethyldiphenylsulfone dihydroxydiarylisatins such as 4,4′-dihydroxydiphenyl-3,3′-isatin;
Dihydroxydiarylxanthenes such as dihydroxy-9,9-dimethylxanthene, resorcinol, 3-phenylresorcinol, 2-t-butylhydroquinone, 2-
Dihydroxybenzenes such as phenylhydroquinone; and dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl.

Among them, 2,2-bis (4-hydroxyphenyl) propane is preferable because of its stability as a monomer, and furthermore, it is easy to obtain although the amount of impurities contained in the monomer is small.

In the present invention, various monomers may be used, if necessary, for controlling the glass transition temperature, improving the fluidity, increasing the refractive index, or controlling the optical properties such as reducing the birefringence. One or more of them can be contained therein.

As specific examples of these, for example,
4-butanediol, 1,4-cyclohexanedimethanol, 1,10-decanediol, 3,9-bis (1,
1-dimethyl-2-hydroxyethyl) -2,4,8,
10-tetraoxaspiro [5,5] undecane, diethylene glycol, polytetramethylene glycol, etc.
Alternatively, dicarboxylic acids, for example, aliphatic dihydroxy compounds such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicaubonic acid, adipic acid, cyclohexanedicarboxylic acid, and p-hydroxybenzoic acid, 6-
Oxy acids such as hydroxy-2-naphthoic acid and lactic acid are exemplified.

The carbonate bond forming precursors include:
In the solution method, a carbonyl halide such as phosgene or a haloformate compound is used. In the melting method, an aromatic carbonate such as diphenyl carbonate or ditolyl carbonate is used. In addition, dimethyl carbonate, dicyclohexyl carbonate and the like can be used if desired. Of these, diphenyl carbonate is preferred from the viewpoints of reactivity, stability against coloring of the obtained polycarbonate, and cost.

A solid phase polymerization method comprising crystallizing a relatively small molecular weight polycarbonate or an oligomer thereof produced by the above-mentioned solution method or melt method, and advancing the polymerization in a solid state at a high temperature (preferably reduced pressure). Can also be preferably used.

In the above-mentioned method for producing a polycarbonate, a dicarboxylic acid derivative such as dicarboxylic acid, dicarboxylic acid halide, dicarboxylic acid or ester, which is an ester-forming precursor, is used in combination with the carbonate bond forming precursor phosgene and carbonic acid diester. The agent of the present invention can also be effectively used for the polyester carbonate containing an ester bond produced by the above method.

Examples of the dicarboxylic acid or dicarboxylic acid derivative of the ester bond forming precursor include terephthalic acid, terephthalic acid chloride, isophthalic acid chloride, and the like.
Aromatic dicarboxylic acid derivatives such as diphenyl terephthalate, diphenyl isophthalate, succinic acid, adipic acid,
Aliphatic dicarboxylic acid derivatives such as dodecane acid, adipic acid chloride, diphenyl decanedioate, diphenyl dodecane diate, 1,3-cyclobutanedicarboxylic acid,
Examples include alicyclic dicarboxylic acid derivatives such as 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid chloride, diphenyl cyclopropanedicarboxylate, and diphenyl 1,4-cyclohexanedicarboxylate.

When producing a polycarbonate having a repeating unit structure represented by the general formula (1), a polyfunctional compound having three or more functional groups in one molecule can be used together with the above dihydroxy compound. . As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferably used.

Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 4,6 dimethyl-2,4,6-tris (4-hydroxyphenyl) -heptane-2,1,
3,5-tris (4-hydroxyphenyl) benzene,
Trimellitic acid, pyromellitic acid and the like can be mentioned.

Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4
-Hydroxyphenyl) -1,3,5-triisopropylbenzene, trimellitic acid and the like can be preferably used.

For example, when a polyfunctional compound is used in combination for the purpose of increasing the melt viscosity of polycarbonate, 0.03 mol or less, preferably 0.00005 to 0.02 mol, more preferably 1 mol, per 1 mol of the aromatic dihydroxy compound. Is selected in the range of 0.0001 to 0.01 mol.

(Catalyst) In the method for producing a polycarbonate having a repeating unit represented by the general formula (1), in the solution method described above, a tertiary amine,
A quaternary ammonium salt, a quaternary phosphonium salt, a nitrogen-containing heterocyclic compound and a salt thereof, an imino ether and a salt thereof, a compound having an amide group, and the like are used.

In this solution method, a large amount of an alkali metal compound or an alkaline earth metal compound is used as a scavenger for hydrogen halide such as hydrochloric acid generated during the reaction.
It is preferable to carry out sufficient washing and purification so that such impurities do not remain in the polymer after production.

In the melting method and the solid phase polymerization method, as the catalyst system, a catalyst system containing an alkali metal compound is preferably used. The amount of the alkali metal to be used is 1 * 10 per mole of the aromatic dihydroxy compound. ^-8 to 1 * 1
0 ^-6 it is important to eq. If the ratio is out of the above range, there are problems that various properties of the obtained polycarbonate are adversely affected, or the transesterification reaction does not sufficiently proceed, and a high molecular weight polycarbonate cannot be obtained.

Examples of the catalyst include alkali metal hydroxides, hydrocarbon compounds, carbonates, nitrates, nitrites, sulfites, cyanates, thiocyanates, organic carboxylate salts, hydrogen carbonates, which are conventionally known as transesterification catalysts. Boron chloride, borohydride, bisphenol, phenol salts, and the like.

Specific examples include sodium hydroxide, lithium carbonate, potassium acetate, rubidium nitrate, sodium nitrite, potassium sulfite, sodium cyanate, sodium thiocyanate, potassium thiocyanate, lithium stearate, sodium borohydride, sodium hydride Lithium boron, sodium phenylated boron, sodium benzoate,
Examples include dipotassium hydrogen phosphate, disodium salt of bisphenol A, monopotassium salt, sodium potassium salt, and sodium salt of phenol.

It is preferable to use a nitrogen-containing basic compound and / or a phosphorus-containing basic compound in combination as a cocatalyst.

Specific examples of the nitrogen-containing basic compound include, for example, tetramethylammonium hydroxide (Me ₄ N
OH), tetrabutylammonium hydroxide (Bu
₄ NOH), alkyl such as benzyl trimethylammonium hydroxide _{(φ-CH 2 (Me)} 3 NOH), aryl, quaternary ammonium hydroxides having an alkyl aryl group, tetramethylammonium acetate, tetraethylammonium phenoxide, tetra Butylammonium carbonate, a basic ammonium salt having an alkyl, aryl, alkylaryl group or the like such as hexadecyltrimethylammonium ethoxide,
Tertiary amines such as triethylamine, or tetramethylammonium borohydride (Me ₄ NB
H ₄ ), basic salts such as tetrabutylammonium borohydride (Bu ₄ NBH ₄ ) and tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ).

Specific examples of the phosphorus-containing basic compound include, for example, tetrabutylphosphonium hydroxide (Bu
Quaternary phosphonium hydroxides having an alkyl, aryl, alkylaryl group or the like such as ₄ POH), benzyltrimethylphosphonium hydroxide (φ-CH ₂ (Me) ₃ POH) and hexadecyltrimethylphosphonium hydroxide, or tetrabutyl phosphonium borohydride (Bu ₄ PBH _4), tetrabutyl phosphonium tetraphenyl borate (Bu ₄ PBPh ₄₎
And the like.

The nitrogen-containing basic compound and / or
Phosphorus basic compounds are basic nitrogen atoms or basic
Atom is 1 * with respect to 1 mole of the aromatic dihydroxy compound.
10 ^-Five~ 5 * 10^-FourIt is preferable to use it at a ratio equivalent to
No. A more preferable usage ratio is 2 * 10 for the same standard.
^-Five~ 5 * 10^-FourThis is the equivalent ratio. Especially preferred
5 * 10 for the same standard^-Five~ 5 * 10^-FourBe equivalent
Percentage.

As the polycarbonate of the present invention, those having a melt viscosity stability of 0.5% or less are preferably used. In order to reduce the melt viscosity stability of the polycarbonate to 0.5% or less, after the desired polycondensation reaction, Or, if desired,
Thereafter, a terminal blocking reaction is further carried out to terminate the reaction, and then a melt viscosity stabilizer (D) may be added to the polycarbonate in a specific amount, for example.

Polycarbonates having inferior melt viscosity stability have the problem of poor mechanical properties under high humidity conditions and long-term use of molded products, in addition to poor stability during molding. In particular, the impact resistance is remarkably reduced, and often does not endure practicality.

(Regarding Melt Viscosity Stabilizer (D)) The melt viscosity stabilizer used in the present invention is selected from the group consisting of phosphonium sulfonate salts and ammonium salts (D).
-1) and / or (S-2) selected from the group consisting of sulfonic acids and lower esters of sulfonic acids.

Specific examples of the compound represented by the above formula (D-1) include, for example, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium benzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, decyl acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium ^{_{salt, - SO 3 - (CH 2}} ) 3 -P + (C 2
H ₅ ) ₃ .

Specific examples of the compound represented by (D-2) include aliphatic sulfonic acids such as aromatic sulfonic acid such as p-toluenesulfonic acid, hexadecylsulfonic acid, butyl benzenesulfonate, p-toluenesulfonic acid and the like. -Butyl toluene sulfonate, ethyl hexadecyl sulfonate, butyl decyl sulfonate and the like. Preferably, an ester compound is used rather than the sulfonic acid itself.

Such a melt viscosity stabilizer is also effective for polycarbonates produced by the phosgene method, but the activity of the basic alkali metal compound remaining in the polycarbonate produced by the melt polymerization method or the solid-state polymerization method. It is effective to reduce With respect to the amount used, for the compound of (D-1), 0.7 to 50 chemical equivalents, preferably 0.8 to 20 chemical equivalents, per chemical equivalent of the alkali metal element of the basic alkali metal compound catalyst. More preferably, 0.9 to 10 chemical equivalents, and in the compound (D-2), 0.7 to 20 chemical equivalents, preferably 0.8 to 10 chemical equivalents, and more preferably 0.9 to 10 chemical equivalents. 5
By using the chemical equivalent, the melt viscosity stability of the polycarbonate can be suppressed to 0.5% or less.

When the melt viscosity stabilizer (D-2) is used, it is preferable to apply a reduced pressure treatment to the polycarbonate that has been subjected to the melt viscosity stabilization treatment.

In performing such a decompression process, the type of the processing apparatus is not particularly limited. On the other hand, when the melt viscosity stabilizer (D-1) is used, there is no need to add such a reduced pressure treatment.

The decompression treatment is performed in a vertical tank reactor, a horizontal tank reactor or a vented single-screw or twin-screw extruder at 0.05 to 60 mmHg, preferably 0.05 to 60 mmHg.
It can be performed under reduced pressure of 〜100 mmHg.

The reduced pressure treatment time is 5 times in the tank type reactor.
Minutes to 3 hours, 5 seconds to 15 when using a twin-screw extruder
Minutes and the processing temperature is preferably from 240 ° C. to 350 ° C.

It is to be noted that pelletizing can be carried out as it is, following the reduced pressure treatment, using an extruder.

By performing the above-described decompression treatment,
The raw material monomers remaining in the polycarbonate are reduced or completely removed.

The phosphonium phosphate compound used in the present invention is at least one selected from a group of phosphonium phosphate compounds having a specific structure represented by the general formula (2).

[0067]

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The flame retardant polycarbonate composition of the present invention is preferably a composition containing the agent represented by the formula (2) in a range of 0.001 to 10 parts by weight based on 100 parts by weight of the polycarbonate. More preferably, 0.005 to 5
Parts by weight, more preferably 0.01 to 1 part by weight.

If the content of the agent is less than 0.001 part by weight, it is difficult to obtain the desired flame retardancy, and if it is more than 10 parts by weight, the heat resistance, particularly the heat resistance at the time of molding tends to decrease.

Further, from the viewpoint of the phosphorus content, the phosphorus component in the phosphonium phosphate salt is desirably 0.0005 to 1 part by weight as a phosphorus element based on 100 parts by weight of the polycarbonate. More preferably 0.001 to 0.5 parts by weight,
More preferably, the composition is contained at 0.005 to 0.3 parts by weight.

In order to further balance the balance between stability and flame retardancy of the polycarbonate composition, the phosphorus component in the phosphonium phosphate salt should be 0.005 to 0.005 as a phosphorus element.
A range of 0.2 parts by weight is more preferred.

Specific examples of the phosphonium phosphate having a specific structure preferably used in the present invention include the following.

(Examples of triphosphonium phosphate) Tris (tetramethylphosphonium) phosphate, tetramethylphosphonium bis (tetraethylphosphonium) phosphate, tetraoctylphosphonium bis (tetrapropylphosphonium), tris (methyltriethylphosphonium) phosphate, bis ( (Tetramethylphosphonium) tetraethylphosphonium, tris (tetrabutylphosphonium) phosphate, tris (diethyldibutylphosphonium) phosphate, tris (tetradecylphosphonium) phosphate, tris (tetraphenylphosphonium), tris (trimethylphenylphosphonium) phosphate, tris (trimethylphenylphosphonium) Tetrabenzylphosphonium) and tris (triethylbenzylphosphonium) phosphate.

(Examples of bisphosphonium phosphate) Potassium bis (tetramethylphosphonium) phosphate, sodium bis (tetramethylphosphonium) phosphate, lithium bis (tetraphenylphosphonium) phosphate, sodium bis (tetrabenzylphosphonium) phosphate, bis (tetramethylphosphonium) phosphate Trimethylbenzylphosphonium) potassium, sodium tetramethylphosphonium tetraethylphosphonium phosphate,
Potassium tetrabutylphosphonium tetraoctylphosphonium phosphate, sodium ethyltrimethylphosphonium tetrabutylphosphonium phosphate, bis (dimethyldiethylphosphonium) phosphate, bis (tetrabutylphosphonium) phosphate, trimethylbenzylphosphonium phosphate, tetrabutylphosphonium tetraoctylphosphonate , Phosphoric acid ethyl trimethyl phosphonium tetrabutyl phosphonium.

(Examples of monophosphonium phosphate) Disodium tetrabutylphosphonium phosphate, sodium potassium tetramethylphosphonium phosphate, dilithium dimethyldiethylphosphonium phosphate, lithium sodium trimethylbenzylphosphonium phosphate, lithium tripropylbutylphosphonium phosphate, sodium trimethyloctylphosphonium phosphate Sodium tetrabutylphosphonium phosphate, potassium tetrapropylphosphonium phosphate, tetraoctylphosphonium diacid phosphate, tetraphenylphosphonium sodium phosphate, ethyl tributylphosphonium sodium phosphate, trimethyloctylphosphonium phosphate lithium, lithium tetramethylphosphonium phosphate, sodium tetraphenylphosphonate sodium, Tetrabenzylphosphonium acid phosphate Thorium, phosphate 2 acid tetramethyl phosphonium, phosphate 2 acid diethyl dibutyl phosphonium, phosphate 2 acid benzyl trimethyl phosphonium, phosphate 2 acidic tetraphenylphosphonium.

(Examples of diester phosphonium phosphate) Dimethyl phosphate (tetrabutyl phosphonium), dinonyl phosphate (dibutyl dioctyl phosphonium), dioctyl phosphate (tetramethyl phosphonium), diphenyl phosphate (tetrabutyl phosphonium), bis (2,4 -Di-t
-Butylphenyl) tetrabutylphosphonium, bis (2,6-di-t-butyl-4-methylphenyl) tetrabutylphosphonium, bis (2,6-di-t-phosphate)
-Butyl-4-methylphenyl) benzyltrimethylphosphonium.

(Examples of Monoester Phosphonium Phosphate) Propyl bis (tetrabutylphosphonium) phosphate, butyl phosphate (tetrabutylphosphonium), sodium phenyl (tetrabutylphosphonium) phosphate, phosphoric acid (2,
6-di-t-butyl-3-methylphenyl) bis (tetramethylphosphonium), potassium (2,6-di-t-butyl-3-methylphenyl) (tetramethylphosphonium) phosphate, acid phosphate (2,6 -Di-t-butyl-3
-Methylphenyl) (tetramethylphosphonium).

Of these phosphonium phosphate salts, triphosphonium phosphate salts and mono- or diester phosphonium phosphate salts are preferred in view of solubility in polycarbonate and thermal stability of a composition containing the compound. In particular, triphosphonium phosphate is preferred from the viewpoint of solubility in polycarbonate and thermal stability of a composition containing the compound.

To further enhance the flame retardancy, it is preferable to use an alkali metal salt of a mono- or diphosphonium phosphate together with the above-mentioned triphosphonium phosphate.

The amount of the alkali metal salt of the mono- or diphosphonium phosphate is 0.001 to 70% by weight based on 100 parts by weight of the total phosphorus content in the compound. Parts. More preferably, it is in the range of 0.005 to 30 parts by weight, more preferably 0.01 to 20 parts by weight.

When an alkali metal salt of mono- or diphosphonium phosphate is used, it is preferable to use mono- or diphosphonium acid phosphate in combination in order to improve the hydrolysis stability of the composition.

At this time, in the case of mono- or diphosphonium phosphate, the acid mono- or diphosphonium is 0.01 to 0.01 mol per mol of the alkali metal element.
It is effective to use it within the range of 5 mol.

In a further preferred embodiment, the polycarbonate is substantially composed of an aryloxy group and a phenolic hydroxyl group as a terminal group structure, and has a phenolic terminal group concentration of 50 mol% or less. The viscosity stability is 0.5% or less.

This is based on the novel finding that when the above-mentioned phosphonium phosphate having a specific structure is used as a flame retardant, the use of such a polycarbonate synergistically enhances the flame retardancy and stability.

In a more preferred embodiment, the polycarbonate has a phenolic terminal group concentration of 40 mol%.
Hereafter, the content is more preferably 30 mol% or less. By introducing a phenolic terminal group at such a ratio, the above object of the present invention is achieved, and at the same time, the moldability when producing a molded article using the flame-retardant polycarbonate composition (in the present specification, Mold fouling and releasability are collectively referred to as simply moldability).

The phenolic terminal group concentration was 5 mol%.
Even if it is further reduced, the further improvement of the physical properties of the flame retardant polycarbonate composition is small. It is obvious from the above discussion that the introduction of a phenolic terminal group concentration exceeding 50% is often undesirable for the purpose of the present invention.

The term "mol%" as used herein for the terminal group concentration refers to the ratio to the total number of moles of the terminal groups of the polycarbonate.

The aryloxy group has 1 to 20 carbon atoms.
Is preferably selected from hydrocarbon-substituted or unsubstituted phenyloxy groups.

From the viewpoint of the heat stability of the polycarbonate composition, the substituent is preferably a tertiary alkyl group, a tertiary aralkyl group, an aryl group, or simply a hydrogen atom. Those having a benzyl-type hydrogen atom can be used if they have a desired purpose such as improvement of actinic radiation resistance, but they should be avoided from the viewpoint of stability against heat, heat aging, thermal decomposition and the like.

Specific examples of preferred aryloxy groups include a phenoxy group, a 4-t-butylphenyloxy group,
There are a 4-t-amylphenyl group, a 4-phenylphenyloxy group, a 4-cumylphenyloxy group and the like.

The melt viscosity stability is an essential factor for controlling the heat resistance, hue, and molecular weight of the polycarbonate composition during melt molding within a favorable range. Such melt viscosity stability can be realized by applying the above-mentioned melt viscosity stabilizer.

In a further preferred embodiment of the present invention, at least one selected from a group of flame-retardant auxiliaries having a specific structure represented by the general formula (3) is used in combination. The stability can be further improved.

Examples of the phosphonium phosphonate represented by the general formula (3) used in the present invention include the following.

(Examples of diphosphonium phosphonates) bis (tetramethylphosphonium) octanephosphonate, tetramethylphosphonium tetraethylphosphonium benzenephosphonate, tetraoctylphosphonium tetrapropylphosphonium benzylphosphonate, bis (methyltriethylphosphonium) nonylphosphonate, Tetramethylphosphonium tetraethylphosphonium toluenephosphonate, bis (tetrabutylphosphonium) methanephosphonate, bis (diethyldibutylphosphonium) butylphosphonate, bis (tetradecylphosphonium) benzenephosphonate, bis (tetraphenylphosphonium) benzenephosphonate, benzene Bis (trimethylphenylphosphonium) phosphonate, bis (tetrabenzylphosphonate) benzyl Honiumu).

(Examples of monophosphonium phosphonate salts) Sodium tetrabutylphosphonium butanephosphonate
Potassium tetramethylphosphonium nonylphosphonate,
Lithium dimethyldiethylphosphonium benzenephosphonate, lithium trimethylbenzylphosphonium benzylphosphonate, lithium tripropylbutylphosphonium cyclohexylphosphonate, sodium trimethyloctylphosphonium naphthalenephosphonate, acidic tetramethylphosphonium hexanephosphonate, acidic tetrabutylphosphonium benzenephosphonate, benzyl Acid tetrapropyl phosphonium phosphonate, tetraoctyl phosphonium naphthalene phosphonate, ethyl tributyl phosphonium octane phosphonate, trimethyl octyl phosphonium toluene phosphonate, tetrabenzyl phosphonium dodecyl phosphonate, diethyl dibutyl phosphonium dodecyl benzene phosphonate,
Acidic benzyltrimethylphosphonium ethanephosphonate.

Of these, diphosphonium phosphonates can be preferably used for the purpose of the present invention.

The flame-retardant polycarbonate composition of the present invention is preferably a composition containing the agent represented by the formula (3) in a range of 0.0001 to 10 parts by weight based on 100 parts by weight of the polycarbonate. More preferably, 0.0005
To 5 parts by weight, more preferably 0.001 to 1 part by weight.

If the content of the agent is less than 0.0001 parts by weight, it is difficult to obtain a synergistic effect with the phosphonium phosphate compound of the formula (2), and if it is more than 10 parts by weight, heat resistance,
In particular, heat resistance at the time of molding tends to decrease.

The amount of the phosphonium phosphonate used is, on a molar basis, P1 / (P1 + P2) = P (P1) based on the phosphorus (P2) of the phosphonium phosphate.
It is in the range of 0.01 to 1, preferably 0.01 to 0.5, and more preferably 0.05 to 0.3.

Further, the present invention will be described below.
Various phosphonium salts such as sulfuric acid and sulfonic acid may be used in combination, if desired.

Examples of the phosphonium sulfate include the following. (Examples of diphosphonium sulfate) bis (tetramethylphosphonium) sulfate, tetramethylphosphonium tetraethylphosphonium sulfate, tetraoctylphosphonium tetrapropylphosphonium sulfate, bis (methyltriethylphosphonium) sulfate, tetramethylphosphonium tetraethylphosphonium sulfate, bis (tetrabutyl) Phosphonium), bis (diethyldibutylphosphonium) sulfate, bis (tetradecylphosphonium) sulfate, bis (tetraphenylphosphonium) sulfate, bis (trimethylphenylphosphonium), bis (tetrabenzylphosphonium) sulfate, bis (triethylbenzylphosphonium) sulfate .

(Examples of monophosphonium sulfate) Sodium tetrabutylphosphonium sulfate, potassium tetramethylphosphonium sulfate, lithium dimethyldiethylphosphonium sulfate, lithium trimethylbenzylphosphonium sulfate, lithium tripropylbutylphosphonium sulfate, sodium trimethyloctylphosphonium sulfate, sodium tetramethyl sulfate, Methylphosphonium, tetrabutylphosphonium sulfate, tetrapropylphosphonium sulfate, tetraoctylphosphonium sulfate, tetraphenylphosphonium sulfate, ethyltributylphosphonium sulfate, trimethyloctylphosphonium sulfate, tetrabenzylphosphonium sulfate, diethyldibutylphosphonium sulfate, Sulfuric acid acidic benzyltrimethylphosphonium, sulfone As the phosphonium salt, for example, tetramethylphosphonium methanesulfonate, dimethyldiethylphosphonium decylsulfonate, tetramethylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium benzylsulfonate, methyltriethylphosphonium nonylsulfonate, p- Tetramethylphosphonium toluenesulfonate, tetrabutylphosphonium decanesulfonate, diethyldibutylphosphonium dodecanesulfonate, tetraphenylphosphonium benzenesulfonate, trimethylphenylphosphonium benzylsulfonate, tetrabenzylphosphonium trifluoromethanesulfonate, triethyl p-toluenesulfonate There is benzylphosphonium.

The amount of the phosphonium salt used is P3 / (P
1) = 0.001-0.5, preferably 0.005-
0.3, more preferably in the range of 0.005 to 0.1.

The polycarbonate composition of the present invention may optionally contain a conventionally known flame retardant.

For example, examples of the phosphate compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropenyl phenyl phosphate, and the like.
Tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) phosphate, and

[0106]

Embedded image

(Where OR ₉ , OR ₁₀ , OR ₁₁ and OR
₁₂ is an alkoxy group such as methoxy, ethoxy, propoxy, or preferably (substituted) phenoxy such as phenoxy, methylphenoxy. T is a divalent or higher valent aromatic residue such as a phenylene group. And polyphosphates such as bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, and trioxybenzene triphosphate.

Preferably, triphenyl phosphate and various aromatic polyphosphates (especially resorcinol polyphosphate or bisphenol A polyphosphate)
It is.

In the present invention, if desired, polytetrafluoroethylene (Teflon (registered trademark)) or the like may be blended as an anti-drip agent.

In the present invention, a polycarbonate composition having excellent durability and stability can be obtained. However, when molding various molded articles using the same, conventionally known processing stabilizers, heat stabilizers, An antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a release agent and the like may be added.

For example, in order to prevent a decrease in molecular weight and a deterioration in hue, if necessary, a usual heat stabilizer such as the following can be added. Specific examples of such a stabilizer include conventionally known phosphorus-based stabilizers, phenol-based stabilizers, organic thioether-based stabilizers, and hindered amine-based stabilizers.

Phosphorus stabilizers include phosphoric acid, phosphorous acid,
Hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, esters thereof, and the like can be used. Examples of the phosphorus-based stabilizer used in the present invention include those commercially available from stabilizer manufacturers as antioxidants.

For example, bis (2,3-di-t-butylphenyl) pentaerythrityl diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythrityl diphosphite, (Nonylphenyl) pentaerythrityldiphosphite, tetra (tridecyl) -4,4′-isopropylidenediphenyldiphosphite, 2,2-methylenebis (4,6-di-t-
Arylalkyl phosphites such as butylphenyl) octyl phosphite, 2- {2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo} d,
f {1,3,2} dioxaphosphepin 6-yl}
Oxy} -N, N-bis {2-} 2,4,8,10-
Tetrakis (1,1 dimethylethyl) dibenzo ｛d,
f {1,3,2} dioxaphosphepin 6-yl}
Arylalkyl phosphites such as oxy {-ethyl} ethanamine, trinonyl phosphite, distearyl pentaerythyl diphosphite, bis (tridecyl)
Pentaerythrityl diphosphite, tris (2,3-
Trialkyl phosphites such as dichloropropyl) phosphite; tricycloalkyl phosphites such as tricyclohexyl phosphite; tris (2,4-di-
triaryl phosphites such as t-butylphenyl) phosphite and tris (nonylphenyl) phosphite; hydrogenated bisphenol-A pentaerythrityl phosphite polymer tridecyl phosphate; distearyl pentaerythrityl diphosphate; 3-
Trialkyl phosphates such as dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphite, tris (2,4-di-
t-butylphenyl) phosphate, tris (nonylphenyl) phosphate, tris (hydroxyphenyl)
Triaryl phosphates such as phosphate, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl) 4,4′-phenylenediphosphinate Phenyl) and the like.

These may be used alone or in combination of two or more. Of these, phosphites are preferred, and aromatic phosphites are particularly preferred. In particular, tris [2,4-di-t-butylphenyl] phosphite or bis (2,4-t-butylphenyl) Pentaerythrityl diphosphite is preferably used.

These heat stabilizers may be used alone or in combination of two or more. The amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 1 part by weight, based on 100 parts by weight of the polycarbonate of the present invention.
0.5 parts by weight is more preferable, and 0.001 to 0.1 parts by weight is further preferable.

Examples of the phenol-based stabilizer include, for example, n
-Octadecyl-3- (4'-hydroxy-3 ', 5'
-Di-t-butylphenyl) propionate, tetrakisdimethylene-3- (3 ', 5'-di-t-butyl-4)
-Hydroxyphenyl) propionate {methane, 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 {, 2,4-bis- (n-octylthio) -6-
(4-hydroxyphenyl 3,5-di-tert-butyl-anilino) -1,3,5-triazine, pentaerythrityl-tetrakis 3- (3,5-di-tert-butyl-4-)
(Hydroxyphenyl) propionate}, 2,2-thiodiethylenebis {3- (3,5-di-tert-butyl-4-)
(Hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-t-butylphenol), N,
N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxy-hydrocinnamamide), 3,5-di-
t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris (3,5-di-t-butyl-
4-hydroxybenzyl) -isocyanurate, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl-2 (4 ′, 8 ′, 12'-trimethyltridecyl) chroman-6-ol, N, N'-bis {3-
(3,5-di-t-butyl-4-hydroxyphenyl)
And propionyl hydrazine.

Examples of the thioether-based stabilizer include dilauryl thiodipropionate, dimyristyl-3,
3'-thiodipropionate, pentaerythritol-
Tetrakis- (β-lauryl-thiopropionate) and the like can be mentioned.

The hindered amine stabilizers include:
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl]- 4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy}-
2,2,6,6-tetramethylpiperidine, 2- (3,
5-di-t-butyl-4-hydroxybenzyl) -2-
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butylmalonate and the like can be mentioned.

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

These heat stabilizer additives are used in an amount of 0.0001 to 5 parts by weight per 100 parts by weight of the polycarbonate component,
It is preferably used in an amount of 0.0005 to 1 part by weight, more preferably 0.001 to 0.5 part by weight.

Further, as the acidic substance scavenger, a compound having one or more epoxy groups in the molecule may be used.

Examples of the acidic substance scavenger include epoxidized soybean oil, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bisphenol A diglycidyl ether, diglycidyl phthalate, 3
-Methyl-5-tert-butyl-1,2-epoxycyclohexane, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate and the like.

Among these, an alicyclic epoxy compound can be preferably used. In particular, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate can be preferably used. Such an epoxy compound is 1 to 2000 p.
m, preferably from 10 to 1000 ppm.

These may be used alone or as a mixture of two or more.

In order to further improve the releasability from the mold at the time of molding, a releasing agent can be added to the polycarbonate composition of the present invention as long as the object of the present invention is not impaired.

As such a release agent, a fatty acid ester-based release agent comprising an aliphatic carboxylic acid and an alcohol can be preferably applied.

For example, a saturated or unsaturated aliphatic mono- or di- or tricarboxylic acid and a saturated or unsaturated monohydric alcohol such as ethanol, butanol or stearyl alcohol, ethylene glycol, 1,4-butenediol, diethylene glycol or the like. Saturated and unsaturated polyhydric alcohols, such as glycerol, unsaturated trihydric alcohols, saturated such as pentaerythritol, unsaturated tetrahydric alcohols, and saturated and unsaturated polyhydric such as pentahydric or higher. Examples include, but are not limited to, esters with alcohols. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid.

[0128] As the preferable release agent, wherein C _n H _2n + 1 -COOH or formula HOOC-C _n H _2n -CO
OH fatty acids with the formula _{C m H 2m + 1 -CH 2} OH, represented by (wherein n is an integer of 5~34) (R1) (R2) C (CH 2 OH) 2, (HOCH 2) _{4 -C, (R3) (CH} 2 OH) 2 C-R4-C (CH 2 OH)
_{2 (R5), (HOCH2)} 3 -C-R4-C- (CH 2 OH) 3 and / or _{HOCH 2 -CH 2 -CH 2 -CH 2} - (CH 2 OH) ( wherein m is from 1 to 20 R1 and R2 each independently represent an alkyl group which may have a substituent having 1 to 10 carbon atoms or a 5- or 6-membered ring (cyclopentyl group or cyclohexyl group) formed by combining R1 and R2. R3 and R5 each independently have 1 to 1 carbon atoms
4 of which may have a substituent group, R4 is an alkylene group having 1 to 4 carbon atoms _{- (CH 2) k -O- (} C
H _{2) k} - (wherein k is to use the esters of the represented) alcohol either by an integer of 1 to 4).

Specific examples of the carboxylic acid represented by the above formula include stearic acid, caproic acid, behenic acid, lignoceric acid cerotic acid, mericinic acid and tetratricontanic acid.

Further, specific examples of the alcohol represented by the above formula include glycerin, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, pentaerythritol, ditrimethylolpropane and the like.

Specifically, pentaerythritol tetrastearate, pentaerythritol tristearate, glycerol tribehenate, glycerol dilaurate, glycerol monostearate, glycerol distearate, trimethylolpropanediolate,
Trimethylolpropane monostearate and the like can be mentioned.

In addition, examples of the hydrocarbon release agent include natural and synthetic paraffin waxes, polyethylene waxes, and fluorocarbons.

Examples of the fatty acid release agent include stearic acid,
Higher fatty acids such as hydroxystearic acid, oxy fatty acids and the like can be mentioned.

Examples of the fatty acid amide type release agent include fatty acid amides such as ethylenebisstearylamide and alkylenebisfatty acid amides such as erucamide.

Examples of the alcohol-based release agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols, and polyglycerols. Other polysiloxanes can also be used.

The compounding amount of the release agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the polycarbonate of the present invention.

(Other Additives) In order to achieve the desired object of the present invention, conventionally known various additives can be used.

For example, as the light stabilizer, 2- (3-t-
Butyl-2-hydroxy-5-methylphenyl) -5
Chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole,
2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) benzotriazole 2- {2-hydroxy-3- (3,4,5 Benzotriazole-based compounds such as 2,6-tetrahydrophthalimidomethyl) phenyl} benzotriazole, benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone,
Benzoate compounds such as 2,4-di-t-butylphenyl and 3,5-di-t-butyl-4-hydroxybenzoate are used as an ultraviolet absorber, for example, ethyl-2.
And cyanoacrylate compounds such as -cyano-3,3-diphenylacrylate.

These light stabilizers and ultraviolet absorbers are usually used in an amount of 0.001 to 5 based on 100 parts by weight of the polycarbonate component.
It can be used in an amount of from 0.05 to 1.0 part by weight, more preferably from 0.01 to 0.5 part by weight. These agents may be used alone or as a mixture.

Examples of the quencher include a nickel-based quencher such as nickel dibutyl dithiocarbamate and {2,2'-thiobis (4-t-octylphenolate)}-2-ethylhexylamine nickel, and a metal deactivator. Is, for example, N, N '-｛3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Compounds such as propionyl dihydrazine, metal soaps such as calcium stearate and nickel stearate, and nucleating agents such as dibenzylidene sorbitol and methylene bis (2,4-
Sorbitol-based and phosphate-based compounds such as sodium di-t-butylphenol acid phosphate).

Examples of the antistatic agent include quaternary ammonium salts such as (β-lauramidopropyl) trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds. .

In the polycarbonate composition of the present invention, an organic or inorganic coloring agent such as a dye or a pigment can be used, if desired.

Specific examples of the inorganic colorant include oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as navy blue, and chromic acids such as zinc chromate. Salts, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal coloring agents such as bronze powder and aluminum powder. .

Examples of the organic colorant include nitrosos such as naphthol green B, nitros such as naphthol yellow S, azos such as naphthol red and chromophtal yellow, and phthalocyanines such as phthalocyanine blue and fast sky blue. And condensed polycyclic colorants such as indanthrone blue.

These coloring agents may be used alone,
Or you may use it by mixing. These colorants are usually 1 * 10 ^{-6 to} 5 per 100 parts by weight of the polycarbonate component.
It can be used in an amount of 1 part by weight, preferably 1 * 10 ^<-6 > to 3 parts by weight, more preferably 1 * 10 ^<-5 > to 1 part by weight.

(Organic and Inorganic Fillers) In addition, inorganic and organic fillers can be added to the polycarbonate of the present invention in order to improve rigidity and the like, as long as the object of the present invention is not impaired.

Examples of the inorganic filler include talc, mica, glass flake, glass beads, calcium carbonate,
Plate-like or granular inorganic filler such as titanium oxide, fibrous filler such as glass fiber, glass milled fiber, wollastonite, carbon fiber, aramid fiber, metallic conductive fiber, crosslinked acrylic particles, crosslinked silicone particles, etc. Organic particles.

The compounding amount of these inorganic and organic fillers is 1 to 1 with respect to 100 parts by weight of the polycarbonate of the present invention.
It is preferably 50 parts by weight, more preferably 3 to 100 parts by weight.

Further, the inorganic filler usable in the present invention may be surface-treated with a silane coupling agent or the like.
By this surface treatment, good results such as suppression of decomposition of polycarbonate can be obtained.

Other resins can be added to the polycarbonate of the present invention as long as the object of the present invention is not impaired.

Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins,
Polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, amorphous polyarylate resin, polystyrene resin, acrylonitrile / styrene copolymer ( AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin,
Resins such as phenolic resins and epoxy resins are exemplified.

From the polycarbonate produced by the present invention, a molded product having good durability and stability can be obtained by an injection molding method or the like.

The polycarbonate composition of the present invention has an effect of maintaining the durability of the polymer composition, particularly the effect of maintaining the long-term durability under severe temperature and humidity conditions, and the antistatic property by applying the above-mentioned specific compounding agent. Compact disk (CD), CD-R obtained using the polymer
Digital versatile discs (DVD-ROM, DVD-Video, DVD-A) such as OM, CD-R, CD-RW, magnet optical disc (MO), etc.
A substrate for a high-density optical disk typified by audio, DVD-R, DVD-RAM, etc. has high reliability over a long period of time. In particular, it is useful for a high-density optical disk such as a digital versatile disk.

The sheet produced from the polycarbonate composition produced according to the present invention is a sheet excellent in adhesiveness and printability in addition to flame retardancy and antistatic properties. Widely used for automobile parts, etc. Specifically, various window materials, ie, glazing products for window materials such as general houses, gymnasiums, baseball domes, vehicles (construction machinery, automobiles, buses, bullet trains, train cars, etc.), and various side walls Boards (sky dome, top light, arcade, apartment lumbar, road side wall), window materials for vehicles, displays and touch panels for OA equipment, membrane switches, photo covers, polycarbonate laminates for water tanks, projection televisions and plasma displays Liquid crystal cell by combining with the front plate, Fresnel lens, optical card, optical disk and polarizing plate. It is useful for optical applications such as the difference between the correction plate or the like.

The thickness of the polycarbonate composition sheet is not particularly limited, but is usually 0.1 to 10 m.
m, preferably 0.2 to 8 mm, and particularly preferably 0.2 to 3 mm. Further, such a polycarbonate composition sheet, various laminating treatment for improving weather resistance, scratch resistance improving treatment for improving surface hardness, surface graining,
Various types of processing for adding new functions such as semi- and opacity processing may be performed.

Further, the polycarbonate composition according to the present invention is also useful when applied to so-called exterior plastic parts of equipment such as housings of various equipment.

[0157] Any method can be employed for blending additives with the polycarbonate of the present invention. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The polycarbonate composition thus obtained is formed into a sheet by a melt extrusion method as it is or after being once pelletized by a melt extruder.

Incidentally, the polycarbonate composition in the present invention means a composition containing the polycarbonate according to the present invention. If this composition contains too many components other than polycarbonate, it impairs the inherent properties of polycarbonate. Therefore, the amount of components other than polycarbonate contained is preferably 1 to 500 parts by weight, more preferably 100 parts by weight of polycarbonate. Ranges from 10 to 200 parts by weight.

From the polycarbonate produced by the present invention, a molded article having good flame retardancy, antistatic properties, dust adhesion preventing property, durability and stability can be obtained by an injection molding method or the like.

[0160]

Industrial Applicability According to the present invention, it is possible to improve the stain resistance due to the adhesion of dust to a molded product without impairing the flame retardancy and mechanical properties, and to provide a flame retardant having excellent thermal stability even during molding. A polycarbonate composition having properties can be provided. Further, it is possible to provide a composition having improved flame retardancy and dust adhesion without impairing the inherent transparency of polycarbonate, and a molded article thereof.

[0161]

Embodiments of the present invention will be described below. In addition,
The present invention is not limited to the following embodiments. In the following, “parts” means “parts by weight” unless otherwise specified. The analysis method used in the following examples is as follows.

(1) Intrinsic viscosity [η] of polycarbonate Measured at 20 ° C. in methylene chloride using an Ubbelohde viscosity tube. The viscosity average molecular weight was calculated from the intrinsic viscosity using the following equation. [Η] = 1.23 × 10 ⁻⁴ Mw ^0.83

(2) Concentration of terminal group 0.02 g of a sample was dissolved in 0.4 mL of chloroform, and 1H-NMR (EX-27 manufactured by JEOL Ltd.) was performed at 20 ° C.
Using 0), the concentrations of terminal hydroxyl groups (ie, phenolic hydroxyl groups) and terminal phenyl groups (ie, aryloxy groups) were measured.

(3) Melt viscosity stability The absolute value of the change in melt viscosity measured at 300 ° C. and a shear rate of 1 rad / sec under a nitrogen stream using a rheometrics RAA type flow analyzer was measured for 30 minutes. The rate of change per minute was determined. For good long-term stability of the polycarbonate composition, it is important that this value does not exceed 0.5%.

(4) Flame retardancy Underwriters Laboratories, Inc. (Underwriters Laboratory)
es Inc. ) Was evaluated in accordance with the "Bulletin Test for Material Classification" (referred to as UL-94 test).
The thickness of the test piece is 1.6 mm. The presence or absence of drip was also determined.

(5) Existence of dust adhesion Box-shaped molded product (85 mm long × 200 mm wide × 15 mm deep)
(X wall thickness 3 mm) was left in a room for 1000 hours, and then surface contamination was visually determined.

(6) Thermal Stability During Molding Processing The hue (color L, a, b) of a hue evaluation plate sample molded under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. using an injection molding machine. The hue (color L ', a', b ') of the hue evaluation plate sample obtained by molding after being kept in a cylinder for 10 minutes was measured with a color difference meter and evaluated by ΔE. ΔE = [(L−L ′) ² + (a−a ′) ² + (b−
b ′) ² ] For the ^1/2 measurement, a Z-1001DP color difference meter manufactured by Nippon Denshoku Co., Ltd. was used.

(7) Transparency, Haze The haze of the flat plate was measured by NDH- # 80 manufactured by Nippon Denshoku Co., Ltd. A lower haze indicates less turbidity.

REFERENCE EXAMPLE 1 (Production of PC-1) Bisphenol A (50,280 g, 221 mol), 7.2% by weight water was placed in a 500 L reactor equipped with a phosgene blowing tube, a thermometer and a stirrer. 221 L of sodium oxide aqueous solution (41 sodium hydroxide
9 mol) and sodium hydrosulfite 98
g (0.56 mol) was dissolved therein, and 127 L of methylene chloride and 8,070 g (98 mol of sodium hydroxide) of a 48.5% by weight aqueous sodium hydroxide solution were added thereto with stirring. Mole) 25
The mixture was added at 180 ° C over 180 minutes to carry out a phosgenation reaction.

After completion of the phosgenation, 930 g (6.2 mol) of p-tert-butylphenol and 48.5% by weight
8,040 g (97 mol) of an aqueous sodium hydroxide solution and 181 mL (1.3 mol) of triethylamine as a catalyst were added, and the mixture was maintained at 33 ° C. and stirred for 2 hours to terminate the reaction. The methylene chloride layer was separated from the reaction mixture, and repeatedly washed with water five times to obtain a polycarbonate having an intrinsic viscosity (η) of 0.46.

REFERENCE EXAMPLE 2 (Production of PC-2) After polymerization in Reference Example 1, the same treatment was carried out except that the number of times of water washing was changed to 3. As a result, a polycarbonate having a melt viscosity stability of 0.7% was obtained. Was. Incidentally, as a result of ion chromatography analysis in the polycarbonate, Na
The ions were contained in an amount of 10 * 10 ^-6 mol per mol of the repeating unit of the polycarbonate.

[Reference Example 3] (Production of PC-3) 1 kg of the polymer obtained in Reference Example 2
0.03 g of tetrabutylphosphonium dodecylbenzenesulfonate (hereinafter abbreviated as DBSP) was added and kneaded into pellets.

Reference Example 4 (Production of PC-4) Bisphenol A (BPA)
8Kg, diphenyl carbonate (DPC) 22.0K
g and 0.004 g of NaOH and 0.91 g of tetramethylammonium hydroxide as polymerization catalysts were charged into a reactor equipped with a stirrer, a distillation column and a decompression device, and after displacing with nitrogen, dissolved at 140 ° C. After stirring for 30 minutes, the internal temperature was raised to 180 ° C., the reaction was performed at an internal pressure of 100 mmHg for 30 minutes, and the phenol produced was distilled off.

Then, the pressure was gradually reduced while the internal temperature was raised to 200 ° C., and the reaction was carried out at 50 mmHg for 30 minutes while distilling off phenol. Further, the temperature was gradually increased and reduced to 220 ° C. and 30 mmHg, and the reaction was performed at the same temperature and the same pressure for 30 minutes. The temperature was further increased to 260 ° C. and 1 mmHg, the pressure was gradually reduced, and the reaction was continued at the same temperature and pressure for 30 minutes.
, The pressure was gradually reduced to 1 mmHg or less, and the reaction was continued under the same temperature and pressure conditions.

Judging from the stirring power of the polymerization reactor finally, when the intrinsic viscosity (η) of the polycarbonate reached 0.46, a part of the polymer was sampled and the terminal hydroxyl group concentration was measured. Thus, the OH terminal group concentration of 70 equivalents /
A polycarbonate of ton polymer (44 mol%) was produced.

Reference Example 5 (Production of PC-5 by End Capping Reaction and Catalyst Inactivation)
14.7 g of a terminal blocking agent (2-methoxycarbonylphenyl-phenyl-carbonate) per 1 kg of the polycarbonate of Reference Example 4 was added at 270 ° C. under a reduced pressure of 50 mmHg. Thereafter, the terminal blocking reaction was continued at 270 ° C. and 1 mmHg or less for 5 minutes.

Thereafter, the melt viscosity stabilizer DBSP0.00
34 g (1.5 equivalents of Na catalyst) was added and mixed and stirred at the same temperature and pressure for 10 minutes to deactivate and deactivate the catalyst.
It was transported to a twin-screw rudder and extruded into chips. The molecular weight, terminal hydroxyl group concentration, and melt viscosity stability of the obtained polycarbonate are shown in the table.

[Examples 1 to 9 and Comparative Examples 1 and 2] (Preparation of polycarbonate composition) Various kinds of agents of the types and amounts shown in the table were added per 100 parts by weight of the polycarbonate produced by the above-mentioned production method, and a super mixer was prepared. With a twin screw extruder having an inner diameter of 50 mm.
The mixture was melt-kneaded under conditions set at 260 ° C. and 260 ° C., extruded and pelletized.

The physical properties of the polymer obtained in each Reference Example, the conditions for adding various agents, and the physical properties of the obtained polycarbonate composition are shown in the table.

[0180]

[Table 1]

[0181]

[Table 2]

[0182]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) G11B 7/24 526 G11B 7/24 526R (72) Inventor Yuichi Kageyama 2-1 Hinodecho, Iwakuni-shi, Yamaguchi Prefecture Teijin Limited Iwakuni Research Center (72) Inventor Katsuji Sasaki 2-1 Hinodecho, Iwakuni-shi, Yamaguchi Prefecture Teijin Limited Iwakuni Research Center F-term (reference) 4F071 AA50 AC15 AE07 AH12 BC01 BC03 BC07 4J002 CG011 CG021 EW176 FD010 FD030 FD040 FD060 FD090 FD100 FD136 FD160 GS02 4J029 AA08 AA09 AB02 AB04 AB07 AC02 AD03 AD10 AE01 AE05 BA02 BA05 BB04A BB04B BB05B BB12A BB12B05 CB13A BB13B 05 CAB09A CB13A CB13A EC06A FC35 FC36 HA01 HB01 HB03A HB04A HB05 HC01 HC04A HC05A JA091 JA121 JA161 JA201 JA261 JA301 JB171 JB201 JC031 JC091 JC121 JC141 JC291 JC311 JC363 JC373 JC631 JC731 JC733 JF021 JF031 JF041 JF051 KE05 KE12 5D029 KA07 KA19 KC09 KC20

Claims (7)

[Claims] 1. A specific structure represented by the following general formula (2) wherein the main repeating unit is a polycarbonate represented by the following general formula (1) and 0.001 to 10 parts by weight per 100 parts by weight of the polycarbonate. A flame-retardant polycarbonate composition comprising at least one selected from the group consisting of phosphonium phosphate compounds having the formula: Embedded image (In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, W is an alkylidene group, an alkylene group,
A cycloalkylidene group, a cycloalkylene group, a phenyl group-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group. ) (In the formula (2), R ₅ , R ₆ , R ₇ , and R ₈ are each independently
Represents an alkyl group, an aralkyl group or an aryl group having 1 to 10 carbon atoms and which may have a substituent. X and Y each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an ammonium base, a phosphonium base or an alkali metal. ) 2. It is preferable that 0.0001 to 5 parts by weight per 100 parts by weight of the polycarbonate contains at least one selected from phosphonium salts of phosphonic acid having a specific structure represented by the following general formula (3). The flame-retardant polycarbonate composition according to claim 1, characterized in that: Embedded image (In the formula (3), R ₄₁ -R ₄₄ are the same as the above R ₅ -R ₈ , Z ₃ is the same as X in the formula (2), and Z is 1-carbon atom which may have a substituent. It represents 20 hydrocarbon groups.) 3. The polycarbonate has a terminal group substantially comprising an aryloxy group and a phenolic hydroxyl group, a phenolic hydroxyl group concentration of 50 mol% or less, and a melt viscosity stability of the polycarbonate of 0.5% or less. The flame-retardant polycarbonate composition according to claim 1 or 2, wherein 4. The polycarbonate is at least one compound selected from the group consisting of a basic nitrogen-containing compound and a basic phosphorus-containing compound from an aromatic dihydroxy compound and a carbonic acid diester, and is selected from the group consisting of an alkali metal compound. The flame-retardant polycarbonate composition according to any one of claims 1 to 3, which is subjected to melt polycondensation in the presence of a catalyst comprising at least one compound. 5. A molded article comprising the polycarbonate composition according to claim 1. 6. The molded article according to claim 5, wherein the molded article is an external plastic part for equipment. 7. The molded article is an optical disk substrate.
The molded article as described.