JP5039848B1 - Flame retardant polycarbonate resin composition and molded product comprising the same - Google Patents

Abstract

The present invention provides a glass fiber reinforced polycarbonate resin composition having excellent flame retardancy and excellent rigidity and strength, and a molded product comprising the same.
A flame retardant polycarbonate resin composition comprising a polycarbonate resin (A), an organic sulfonic acid metal salt (B), a compound having an inclusion ability (C), and a glass fiber (E). .
[Selection figure] None

Description

  The present invention relates to a flame retardant polycarbonate resin composition and a molded article comprising the same, and more particularly to a flame retardant polycarbonate resin composition having excellent flame retardancy and excellent rigidity and strength and a molded article comprising the same.

  Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. In particular, the flame-retardant polycarbonate resin composition is suitably used as a member of OA / information equipment such as computers, notebook computers, mobile phones, printers, and copying machines.

As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin.
However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were. In addition, the polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the polycarbonate resin and causes a decrease in impact resistance and heat resistance, so that its use is limited. was there. In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.

  Under such circumstances, in recent years, many metal salt compounds typified by organic alkali metal salt compounds and organic alkaline earth metal salt compounds have been studied as useful flame retardants. When an organometallic salt compound is used as a flame retardant, the effect can be obtained in a relatively small amount, and it is difficult without impairing the mechanical properties such as impact resistance, heat resistance, and electrical properties inherent to the polycarbonate resin. This is because flammability can be imparted.

  Examples of the flame-retarding technology of polycarbonate using a metal salt compound include, for example, a method using an alkali metal salt of perfluoroalkyl sulfonic acid having 4 to 8 carbon atoms (see Patent Document 1), and perfluoroalkane sulfone having 1 to 3 carbon atoms. A method of imparting flame retardancy to an aromatic polycarbonate resin using an alkali metal salt compound of perfluoroalkanesulfonic acid, such as a method of blending an alkali metal salt of an acid (see Patent Document 2); Using an alkali metal salt compound of an aromatic sulfonic acid such as a method of containing an acid sodium salt (see Patent Document 3) and a method of containing a non-halogenated aromatic sulfonic acid potassium salt (see Patent Document 4) A technique for imparting flame retardancy to a polycarbonate resin composition has been proposed.

  These metal salt flame retardant compounds are relatively good flame retardant for polycarbonate resins and are excellent flame retardants. However, when a metal salt-based flame retardant is added to a glass fiber reinforced polycarbonate resin material in which glass fiber is blended with polycarbonate resin, there is a problem that the strength and rigidity of the polycarbonate resin are reduced.

Japanese Patent Publication No. 47-40445 Japanese Patent Publication No.54-32456 JP 2000-169696 A JP 2001-181493 A

  As described above, the flame retardancy by the metal salt compound is not sufficient in the case of the glass fiber reinforced polycarbonate resin, and the present invention has been made in view of such problems, and has excellent flame retardancy and rigidity. It aims at providing the glass fiber reinforced polycarbonate resin composition excellent in strength.

As a result of intensive investigations to achieve the above-mentioned problems, the present inventor has excellent flame retardancy and rigidity when the glass fiber-reinforced polycarbonate resin contains a metal salt compound and a compound having an inclusion ability. It was found that a glass fiber reinforced polycarbonate resin excellent in strength was obtained, and the present invention was completed.
That is, the present invention provides the following flame retardant polycarbonate resin composition and a molded product formed by molding the same.

[1] The polycarbonate resin (A) relative to 100 parts by weight, perfluoroalkanesulfonic acid alkali metal salt (B) 0.01 to 2 parts by weight, crown ether compound (C) 0.01 to 2 parts by mass of glass fibers ( E) The flame-retardant polycarbonate resin composition characterized by containing 3-80 mass parts .
[2] above wherein at least a portion of the crown ether compound of perfluoroalkane sulfonic acid alkali metal salt (B) at least a portion of (C) is characterized in that it forms the inclusion complex (D) in contact follicles The flame-retardant polycarbonate resin composition according to [1].

[ 3 ] The flame-retardant polycarbonate according to [1] or [ 2 ], further comprising 0.001 to 1 part by mass of a fluoropolymer (F) with respect to 100 parts by mass of the polycarbonate resin (A). Resin composition.
[4] alkali metal perfluoroalkane sulfonate alkali metal salt, K, Na, flame retardant polycarbonate resin composition according to any one of the above [1] to [3], which is a Cs or Li object.

[ 5 ] A molded product formed by molding the polycarbonate resin composition according to any one of [1] to [ 4 ].

In the polycarbonate resin composition of the present invention, the polycarbonate resin composition reinforced with glass fibers is clathrated with a compound having an inclusion ability of the organic sulfonic acid metal salt, so that the organic sulfonic acid metal salt becomes oil-soluble, The compatibility with polycarbonate resin is greatly improved, and the organic sulfonic acid metal salt has a complex structure, so that ionization of the organic sulfonic acid metal salt can be promoted, and a flame-retardant effect can be achieved with a smaller amount of addition. , A decrease in rigidity and strength is suppressed.
Therefore, the polycarbonate resin composition of the present invention can provide a glass fiber reinforced polycarbonate resin composition having excellent flame retardancy and excellent rigidity and strength.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In addition, in this-application specification, unless there is particular notice, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[1. Overview]
The polycarbonate resin composition of the present invention is characterized in that the polycarbonate resin (A) containing glass fiber (E) contains an organic sulfonic acid metal salt (B) and a compound (C) having an inclusion ability. .

[2. Polycarbonate resin (A)]
Examples of the polycarbonate resin (A) of the resin material used in the present invention include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins, preferably aromatic polycarbonate resins. A thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is used.

Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, 2,2 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxy- 3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methoxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4 -Hydroxy-3- (1-methylethyl) phenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propyl Bread, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane, 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy) -3-phenylphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane Bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1 -Bis (4-hydroxy-3- (1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy) 3-tert-butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1, 1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3, 5- Dimethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butyl) Phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-pheny Ruethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis ( 4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-pheny Range isopropylidene) bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxy Phenyl ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfo Xoxide, bis (4-hydroxyphenyl) sulfone, 4,4′-dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1,1-bis (4-hydroxy-) 6-methyl-3-tert-butylphenyl) butane, hydroquinone, resorcinol, and the like. Examples of the aliphatic dihydroxy compound include tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, 1,4- Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,5-norbornanedimethanol, 2,6-norbornanedimethanol, trans-2,6-decalindimethanol, 1,4-cyclohexanediol, 2,2,4 , 4, -Tetramethylcyclopropanediol, 1,4-butanediol 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Examples include decanediol, 1,11-undecanediol, and 1,12-dodecanediol. Further, as a part of the dihydroxy compound, when a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the dihydroxy compound, or a polymer or oligomer having a siloxane structure and containing both terminal phenolic OH groups is used, flame retardancy A highly polycarbonate resin can be obtained.

  Preferred examples of the polycarbonate resin (A) used in the present invention include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy. The polycarbonate resin which used the compound together is mentioned. In the present invention, two or more polycarbonate resins may be used in combination as the component (A).

  The molecular weight of the polycarbonate resin used in the present invention is not limited, but it is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 10,000 to 40,000. Preferably it is 14,000-32,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be obtained. The most preferred molecular weight range of the polycarbonate resin is 16,000 to 30,000.

  The production method of the polycarbonate resin (A) is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can be used. Moreover, it is also preferable to use the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method.

  The polycarbonate resin (A) is not limited to an embodiment including only one type of polycarbonate resin, and includes an embodiment including a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the sense) or may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  In addition, the polycarbonate resin (A) may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate oligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin (A) may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[3. Organic sulfonic acid metal salt (B)]
An organic sulfonic acid metal salt (B) is used in the resin composition of the present invention.
The types of metals possessed by organic sulfonic acid metal salts include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); magnesium (Mg), calcium (Ca ), Alkaline earth metals such as strontium (Sr), barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Zinc (Zn), zirconium (Zr), molybdenum (Mo) and the like can be mentioned, among which alkali metals or alkaline earth metals are preferable. Promotes the formation of a carbonized layer during the combustion of polycarbonate resin, further enhances flame retardancy, and maintains good properties such as impact resistance and other mechanical properties, heat resistance, and electrical properties of polycarbonate resin Because it can.
Of the alkali metals or alkaline earth metals, alkali metals are more preferred, sodium, potassium, cesium or lithium are more preferred, sodium, potassium and cesium are more preferred, and sodium and potassium are particularly preferred.

  Examples of such organic sulfonic acid metal salt (B) include lithium organic sulfonate (Li) salt, organic sodium sulfonate (Na) salt, organic potassium sulfonate (K) salt, organic rubidium sulfonate (Rb). ) Salt, organic sulfonic acid cesium (Cs) salt, organic sulfonic acid magnesium (Mg) salt, organic sulfonic acid calcium (Ca) salt, organic sulfonic acid strontium (Sr) salt, organic sulfonic acid barium (Ba) salt, etc. Can be mentioned. Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt compound, and organic sulfonic acid cesium (Cs) salt compound are particularly preferable.

  Among the organic sulfonic acid metal salts (B), preferred are fluorine-containing aliphatic sulfonic acid metal salts, fluorine-containing aliphatic sulfonic acid imide metal salts, aromatic sulfonic acid metal salts, and aromatic sulfonamide. Metal salts are mentioned.

  Among them, specific examples of preferable ones include potassium nonafluorobutanesulfonate, lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, cesium nonafluorobutanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, Containing at least one C—F bond in the molecule, such as potassium trifluoromethanesulfonate, potassium pentafluoroethanesulfonate, potassium heptafluoropropanesulfonate, potassium decafluoro-4- (pentafluoroethyl) cyclohexanesulfonate; Alkali metal salts of fluoroaliphatic sulfonic acids;

  At least one C—F in the molecule, such as magnesium nonafluorobutanesulfonate, calcium nonafluorobutanesulfonate, barium nonafluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, barium trifluoromethanesulfonate, etc. An alkaline earth metal salt of a fluorine-containing aliphatic sulfonic acid having a bond;

  Disodium difluoromethane disulfonate, dipotassium difluoromethane disulfonate, disodium tetrafluoroethane disulfonate, dipotassium tetrafluoroethane disulfonate, dipotassium hexafluoropropane disulfonate, dipotassium hexafluoroisopropane disulfonate, disodium octafluorobutane disulfonate An alkali metal salt of a fluorinated aliphatic disulfonic acid having at least one C—F bond in the molecule, such as dipotassium octafluorobutanedisulfonate; a metal salt of a fluorinated aliphatic sulfonic acid, such as

  Bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide sodium, In the molecule, such as potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane, etc. An alkali metal salt of a fluorine-containing aliphatic disulfonic imide having at least one C—F bond;

  Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorinated aliphatic sulfonimide having at least one C—F bond in the molecule; a metal salt of a fluorinated aliphatic sulfonic imide, such as

  Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate Etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule;

  Magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) calcium dodecylbenzenesulfonate in the molecule An alkaline earth metal salt of an aromatic sulfonic acid having an aromatic group of: an aromatic sulfonic acid metal salt, etc.

  Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonamides such as alkali metal salts of aromatic sulfonamides having at least one aromatic group in the molecule, such as salts.

Among the examples described above, fluorine-containing aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts are more preferable, and fluorine-containing aliphatic sulfonic acid metal salts are particularly preferable.
The fluorine-containing aliphatic sulfonic acid metal salt is more preferably an alkali metal salt of a fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule, and particularly preferably an alkali metal salt of perfluoroalkanesulfonic acid. Specifically, potassium nonafluorobutanesulfonate is preferred.
As the aromatic sulfonic acid metal salt, an alkali metal salt of an aromatic sulfonic acid is more preferable, and diphenylsulfone-sulfonic acid alkali metal such as diphenylsulfone-3,3′-disulfonic acid dipotassium, diphenylsulfone-3-sulfonic acid potassium, etc. Particularly preferred are salts; sodium paratoluenesulfonate, and alkali metal salts of paratoluenesulfonic acid such as potassium paratoluenesulfonate and cesium paratoluenesulfonate, and more preferably alkali metal salts of paratoluenesulfonic acid.

  In addition, 1 type may be used for organic sulfonic acid metal salt (B), and it may use 2 or more types together by arbitrary combinations and a ratio.

[4. Compound (C) having inclusion ability]
In the polycarbonate resin composition of the present invention, a compound (C) having an inclusion ability is used.
The compound (C) having an inclusion ability means a compound that can take in the metal cation of the organic sulfonic acid metal salt (B) and activate the counter anion.
The compound (C) having an inclusion ability includes cyclic polyether, cyclic polyether polyester, cyclic polyketone, cyclic polyamine, cyclic polyamine polyamide, cyclic polythiaether, azacrown ether, thiacrown ether, cyclic azathiacrown ether, aza Preference is given to at least one compound selected from the group consisting of thiacrown ether, bicyclic cryptand, tricyclic cryptand and spherical cryptand.
Of these, cyclic polyethers are preferable, and crown ether compounds are particularly preferable.

In the present invention, the crown ether compound means a crown ether and a derivative having a crown ether structure. The crown ether compound is a compound having a ring having a repeating unit of [—CH ₂ —CH ₂ —Y—], and —CH ₂ —CH ₂ — forming the ring may be substituted. Is a heteroatom of O, N, S. Examples of the crown ether compound include crown ether, thiacrown ether in which oxygen is substituted with sulfur, azacrown ether substituted with nitrogen, cryptand which is a bicyclic crown ether, among them, crown ether and azacrown ether And crown ether is particularly preferable.
Such a crown ether compound has an ability to form a complex compound by capturing a metal cation of an organic sulfonic acid metal salt in the ring because an oxygen atom or the like is negatively charged inside the ring.

  Specifically, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, 21-crown-7-ether, 24-crown-8-ether, 30-crown-10 -Crown ethers such as ether, and dibenzo-18-crown-6-ether, dibenzo-14-crown-4-ether, dibenzo-15-crown-5-ether, dibenzo-12-crown-4-ether, dibenzo -21-crown-7-ether, dibenzo-24-crown-8-ether, dibenzo-30-crown-10-ether, benzo-18-crown-6-ether, benzo-15-crown-5-ether, benzo -12-crown-4-ether, tribenzo-24-crown-8-ether, dicycl Hexyl-12-crown-4-ether, dicyclohexyl-15-crown-5-ether, dicyclohexyl-18-crown-6-ether, n-octyl-12-crown-4-ether, n-octyl-15-crown- Examples include crown ether derivatives such as 5-ether and n-octyl-18-crown-6-ether, and other crown ethers such as lariat having a long chain on the crown and cryptand which is a bicyclic crown.

  Examples of azacrown ether include 1-aza-15-crown-5, 1-aza-18-crown-6, 4,10-diaza-12-crown-4, 4,10-diaza-15 Crown-5, 4,13-diaza-18-crown-6, N, N′-dibenzoyl-4,13-diaza-18-crown-6, N-phenylaza-15-crown-5 and the like.

  In the present invention, among these crown ether compounds, it is preferable to use 15-crown-5-ether, 18-crown-6-ether, or dibenzo-18-crown-6-ether. Is preferable because it easily forms a complex with these ions from the viewpoint of the cation ion size of the preferred potassium salt or sodium salt as the organic sulfonic acid metal salt.

[4. Inclusion Compound of Organic Sulfonate Metal Salt (B) and Compound (C) Having Inclusion Capability]
The flame retardant of the present invention comprises an inclusion compound of the above organic sulfonic acid metal salt and the above crown ether compound. The crown ether compound has a function of incorporating a metal cation of an organic sulfonic acid metal salt to form a stable complex. Since the polar vacancies of this crown ether take in cations having an ionic diameter suitable for the vacancy diameter into the vacancies, it is preferable to select the crown ether compound to be used depending on the metal cation species. For example, 18-crown-6-ether or dibenzo-18-crown-6-ether is preferably used in the case of potassium salt as the organic sulfonic acid metal salt, and 15-crown-5-ether in the case of sodium salt. Is preferably used.
The organic sulfonic acid metal salt is originally hydrophilic and has low compatibility with the polycarbonate resin. However, the organic sulfonic acid metal salt is obtained by inclusion of the organic sulfonic acid metal salt in a crown ether compound to form an inclusion compound. Becomes oil-soluble under the influence of the crown ether compound, and the compatibility with the polycarbonate resin is greatly improved. Therefore, when the organic sulfonic acid metal salt has a complex structure with the crown ether compound, ionization of the organic sulfonic acid metal salt can be promoted, and a flame-retardant effect can be achieved with a smaller amount of addition.

As a matter of course, the organic sulfonic acid metal salt (B) and the compound (C) having an inclusion ability may be included in the polycarbonate resin (A) as an inclusion compound in which both are included in advance. .
The clathrate compound of the organic sulfonic acid metal salt (B) and the clathrate compound (C) is not limited to those in which they form a clathrate compound in a molar ratio of 1: 1. In various forms other than equimolar, such as those in which a metal cation of an organic sulfonic acid metal salt is coordinated by some interaction between polar vacancies of a plurality of crown ether compounds It may be.

The clathrate compound may be produced by any method known in the art by using the organic sulfonic acid metal salt (B) and the clathrate compound (C). For example, the organic sulfonic acid metal salt (B) and the compound (C) having inclusion ability may be mixed or stirred using water, hot water or an organic solvent as necessary, or mixed and stirred while heating to a desired temperature. Can be manufactured. As the organic solvent, a solvent such as an aromatic hydrocarbon compound, an aliphatic hydrocarbon compound, an alcohol compound, a ketone compound, an ester compound, or a terpene compound is used alone or as a mixed solvent. Specific examples include acetone, toluene, xylene, hexane, heptane, kerosene, methanol, ethanol, 2-propanol, n-butanol, ethyl acetate, propyl acetate, and butyl acetate.
When the obtained inclusion compound is difficult to dissolve in water or an organic solvent, it can be separated by heating to a homogeneous solution and then cooling.

As a simple and preferable method for producing an inclusion compound, the organic sulfonic acid metal salt (B) and the compound (C) having an inclusion ability can be mixed in water or warm water. When the clathrate compound produced is difficult to dissolve in water, the clathrate compound can be obtained by heating to a homogeneous solution and then cooling to separate into two phases.
Moreover, it is also preferable to supply the clathrate compound containing water at this time together with other resin additives to a kneader for producing a polycarbonate resin composition as it is.
Furthermore, a small amount of water, the organic sulfonic acid metal salt (B), the compound (C) having inclusion ability, and other resin additives are mixed, and the resulting aqueous solution is heated and stirred. A mixture of the resin (A) and flaked is also preferable, and this can be fed to a kneader or the like as it is.

  In each of these methods or in the polycarbonate resin composition, the content of the organic sulfonic acid metal salt (B) and the compound (C) having an inclusion ability is such that the molar ratio ((B) / (C)) It is preferably 10/1 to 1/10, more preferably 5/1 to 1/5, further preferably 3/1 to 1/3, particularly preferably 2/1 to 1/2, and most preferably 1. .5 / 1 to 1 / 1.5.

  In the polycarbonate resin composition, the content of the organic sulfonic acid metal salt (B) is preferably 0.01 parts by mass or more, preferably 0.02 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). More preferably 0.03 parts by mass or more, further preferably 0.04 parts by mass or more, particularly preferably 0.05 parts by mass or more, and the upper limit is 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0. 0.5 parts by mass or less, particularly preferably 0.3 parts by mass or less. If the content is too small, the flame retardancy may be insufficient. On the other hand, if the content is too large, the thermal stability and hydrolysis resistance of the polycarbonate resin are lowered, and the color tone tends to deteriorate.

  In the polycarbonate resin composition, the content of the compound (C) having an inclusion ability is preferably 0.01 parts by mass or more, preferably 0.02 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). More preferably 0.03 parts by mass or more, still more preferably 0.04 parts by mass or more, particularly preferably 0.05 parts by mass or more, and the upper limit is 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, particularly preferably 0.3 parts by mass or less. If the content is too small, the effect may be insufficient. On the other hand, if the content is too large, appearance defects may occur in the molded product, or the mold may be contaminated during injection molding.

  In addition, the preferable content of the inclusion compound of the organic sulfonic acid metal salt (B) and the compound (C) having an inclusion ability is 0.005% by mass or more, preferably 0.01% by mass with respect to the polycarbonate resin. % Or more, more preferably 0.02 mass% or more, further preferably 0.03 mass% or more, particularly preferably 0.04 mass% or more, and the upper limit is 1 mass% or less, preferably 0.7 mass% or less. More preferably, it is 0.5% by mass or less, particularly preferably 0.3% by mass or less. If the content is too small, the flame retardancy may be insufficient. On the other hand, if the content is too large, the thermal stability of the polycarbonate resin may decrease, and the appearance of the molded product may deteriorate and the mechanical strength may decrease. There is sex.

[5. Glass fiber (E)]
Any glass fiber (E) used in the present invention can be used as long as it is usually used in thermoplastic resins, but alkali-free glass (E glass) is preferred. The number average fiber length of the glass fiber (E) is preferably 1 mm or more and 10 mm or less, and the diameter of the glass fiber is preferably 5 μm or more and 20 μm or less. These can be produced by pulverizing glass fiber strands using, for example, a hammer mill or a ball mill according to any conventionally known method.

If the number average fiber length exceeds 10 mm, the glass fibers and carbon black are likely to fall off from the surface of the molded product, and the productivity tends to decrease. If the number average fiber length is less than 1 mm, the glass fiber has a small aspect ratio, and therefore mechanical strength is likely to be insufficiently improved.
Similarly, when the diameter of the glass fiber is less than 5 μm, the improvement of the mechanical strength is similarly insufficient, and when it exceeds 20 μm, the appearance tends to deteriorate. The diameter of the glass fiber is more preferably 6 μm or more and 15 μm or less.

  The polycarbonate resin composition of the present invention is flame retardant with a small amount of flame retardant by using in combination with the above-described organic sulfonic acid metal salt (B), compound (C) having inclusion ability, and glass fiber (E). There is a remarkable effect that The reason for this is that when the combustion propagates through the glass fiber in the resin composition, the organic sulfonic acid metal salt (B) compatibilized and finely dispersed in the resin and the compound (C) having an inclusion ability It is considered that the clathrate compound gathers in the vicinity of the glass fiber to exert a strong flame-extinguishing effect, and the combustibility is lowered because the propagation of combustion is hindered.

  The glass fiber (E) used in the present invention can be subjected to a surface treatment with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion to the polycarbonate resin.

[6. Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include heat stabilizers, antioxidants, mold release agents, anti-dripping agents, other flame retardants, UV absorbers, dyes and pigments, fluorescent whitening agents, antistatic agents, antifogging agents, lubricants. , Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like.

-Heat stabilizer As a heat stabilizer, a phosphorus compound is mentioned, for example. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphinic acid and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate and acidic calcium pyrophosphate; potassium phosphate, phosphorus Examples include Group 1 or Group 10 metal phosphates such as sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) Organic phosphites such as octyl phosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are preferred.

  The content of the heat stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, based on 100 parts by mass of the polycarbonate resin. It is not more than part by mass, preferably not more than 0.7 part by mass, more preferably not more than 0.5 part by mass. If the amount of the heat stabilizer is too small, the heat stability effect may be insufficient. If the amount of the heat stabilizer is too large, the hydrolysis resistance may be reduced, or the effect may reach its peak and become less economical.

-Antioxidant As an antioxidant, a hindered phenolic antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the polycarbonate resin. Or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

-Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. It is done.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol tetraoleate, etc. It is done.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the polycarbonate resin. It is. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

-Anti-dripping agent It is preferable that the polycarbonate resin composition of this invention contains 0.01-1 mass part of fluororesins as an anti-dripping agent with respect to 100 mass parts of polycarbonate resin. By containing the fluororesin in this manner, the melting characteristics of the resin composition can be improved, and specifically, the dripping prevention property at the time of combustion can be improved.

  If the content of the fluororesin is less than 0.01 parts by mass, the effect of improving the flame retardancy due to the fluororesin tends to be insufficient, and if it exceeds 1 part by mass, a molded product obtained by molding a thermoplastic resin composition. The appearance defect and the mechanical strength are likely to decrease. The lower limit of the content is more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, particularly preferably 0.2 parts by mass or more, and the upper limit of the content is more preferably 0. .75 parts by mass or less, more preferably 0.6 parts by mass or less, and particularly preferably 0.5 parts by mass or less.

Of these, fluoroolefin resins are preferred as the fluororesin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and those produced by a suspension polymerization method or an emulsion polymerization method are mainly used. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like, among which tetrafluoroethylene resin is preferable.
Moreover, as this fluororesin, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Examples of the fluoroolefin resin having fibril-forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon (registered trademark) F201L” manufactured by Daikin Chemical Industries, Ltd. "," Polyflon (registered trademark) FA500 "and the like. Furthermore, as commercially available products of aqueous dispersions of fluoroolefin resins, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon ( Registered trademark) D-1 "and the like.

  Furthermore, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. And the like, and the like.

The organic polymer for coating the fluoroolefin resin is not particularly limited, and specific examples of monomers for producing such an organic polymer include styrene, α-methylstyrene, p. -Methylstyrene, o-methylstyrene, tert-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4- Aromatic vinyl monomers such as dimethylstyrene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, (Meth) acrylic acid ester monomers such as tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate;

Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Α, β-unsaturated carboxylic acids such as maleic anhydride; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide;
Glycidyl group-containing monomers such as glycidyl methacrylate;
Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate;
Olefinic monomers such as ethylene, propylene, isobutylene;
Examples thereof include diene monomers such as butadiene, isoprene and dimethylbutadiene. In addition, these monomers can be used individually or in mixture of 2 or more types.

  Among them, as a monomer for producing an organic polymer covering a fluoroolefin resin, those having a high affinity with an aromatic polycarbonate resin are preferable from the viewpoint of dispersibility when blended with an aromatic polycarbonate resin. An aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a vinyl cyanide monomer are more preferable.

  The content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is usually 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Usually, it is 95 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, Most preferably, it is 75 mass% or less. It is preferable that the content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is in the above-described range because the balance between the flame retardancy and the appearance of the molded product tends to be excellent.

As such an organic polymer-coated fluoroolefin resin, specifically, “Metabrene (registered trademark) A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex (registered trademark) 449” manufactured by GE Specialty Chemical Co., Ltd., PIC Company "Poly TS AD001" manufactured by the company etc. are mentioned.
In addition, 1 type may contain fluorine-type resin, and 2 or more types may contain it by arbitrary combinations and a ratio.

[7. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, Glass fiber (E) and organic sulfonic-acid metal salt (B ) And the compound (C) having an inclusion ability, either as they are or as an inclusion compound in advance, and other components added as necessary, such as a tumbler, a Henschel mixer, a super mixer, a ribbon blender, etc. Examples thereof include a method in which the various types of mixers are mixed in advance and then melt kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like. A method of mixing the glass fiber (E) after previously melting and mixing the polycarbonate resin (A), the organic sulfonic acid metal salt (B), the compound having inclusion ability (C), and an additive component blended as necessary. However, this is a more preferable mixing method from the viewpoint of preventing the glass fibers from being crushed.
The temperature for melt kneading is not particularly limited, but is usually in the range of 220 to 360 ° C.
In addition, as described above, a small amount of water, an organic sulfonic acid metal salt and a crown ether compound, and other resin additives are mixed, and an aqueous solution obtained by heating and stirring the mixture is mixed with a polycarbonate resin. It is also preferable to obtain flakes and feed them to a kneader or the like.

[8. Molding]
The polycarbonate resin composition of the present invention can be produced by molding pelletized pellets by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets.
Examples of molding methods include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating molds. Molding method used, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. A molding method using a hot runner method can also be used. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  Examples of preferable molded articles obtained by molding the composition of the present invention include lighting equipment, electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods and miscellaneous goods. And the like. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, and home appliances.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
[Polycarbonate resin]
In Examples and Comparative Examples, the following polycarbonate resin was used as the polycarbonate resin (A). In the table, it is expressed as “PC”.
Product name "Iupilon (registered trademark) S-3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Viscosity average molecular weight 21,000

Moreover, the following glass fiber was used as glass fiber (E). In the table, it is expressed as “GF”.
Product name “CS03MAFT737” manufactured by Owens Corning Japan
Number average fiber length 3mm, average diameter 13μm
Further, as the polytetrafluoroethylene resin, a product name “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd. was used. In the table, it is expressed as “PTFE”.

Example 1
[Production of resin composition pellets]
70 parts by mass of the polycarbonate resin, 0.1 part by mass of pentaerythritol tetrastearate as a release agent, 0.1 part by mass of stearyl stearate, 0.1 part by mass of the polytetrafluoroethylene resin, and 30 parts by mass of glass fiber In addition, 0.075 parts by mass of potassium nonafluorobutanesulfonate (C ₄ F ₉ SO ₃ K) and 0.0586 parts by mass of 18-crown-6-ether (nonafluorobutanesulfone) in 1 part by mass of water Potassium acid and 18-crown-6-ether are equimolar amounts.) Are heated and dissolved at 95 ° C., stirred for 20 minutes, allowed to cool to 25 ° C., and further stirred to obtain a homogeneous aqueous solution. It prepared and it mixed uniformly except the glass fiber with the tumbler, and it was set as the flaky raw material. The flaky raw material and glass fiber were melt-kneaded as follows.
That is, in a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (TEM37BS) having one vent having a base raw material inlet, a side feed port and a die, a speed of 21.1 kg / hr based on the above flaky raw material, glass The fiber is side-fed at a speed of 9.0 kg / hr, kneaded under the conditions of a screw speed of 300 rpm, a discharge rate of 30.1 kg / hr, and a barrel temperature of 280 ° C. Quenched and pelletized using a pelletizer to obtain pellets of polycarbonate resin composition.

[(1) Flame retardant evaluation (UL)]
The obtained pellets were dried at 120 ° C. for 6 hours, and then injection-molded under the conditions of a mold temperature of 80 ° C. and a cylinder set temperature of 290 ° C. using an injection molding machine J50 manufactured by Nippon Steel Works, a length of 125 mm, A test piece for combustion test having a width of 13 mm and a thickness of 2.5 mm was obtained.
About the obtained test piece for a combustion test, the vertical combustion test based on UL94V was performed, the flammability result was set to V-0, V-1, V-2 from the favorable order, and the thing outside the standard was classified as NG. .

[(2) Maximum tensile strength and tensile modulus]
Using the resin composition pellets obtained by the above method, the cylinder temperature was 290 ° C. and the mold temperature was 110 at an injection molding machine (“SG75 Cycap M-2”, manufactured by Sumitomo Heavy Industries, Ltd., clamping force 75 t). An ISO multipurpose test piece (thickness 4 mm) was produced under the condition of ° C. Using the obtained ISO test piece, the maximum tensile strength (unit: MPa) and the tensile modulus (unit: MPa) were measured at a temperature of 23 ° C. in accordance with ISO standard 527-1 and ISO 527-2.

[(3) Flexural strength, flexural modulus]
Bending strength (unit: MPa) and bending elastic modulus (unit: MPa) at a temperature of 23 ° C. in accordance with ISO178 using a bending test piece (thickness 4 mm) manufactured in the same manner as (2) above. Was measured.
The above evaluation results are shown in Table 1.

(Example 2)
In Example 1, potassium nonafluorobutanesulfonate _{(C 4 F 9 SO 3 K} ) and 18 amounts crown-6 the amount of ether in Table 1 (and potassium nonafluorobutanesulfonate 18-crown-6 The same procedure as in Example 1 except that the amount of ether is an equimolar amount. The evaluation results are shown in Table 1.

(Example 3)
In Example 1, the amount of potassium nonafluorobutanesulfonate (C ₄ F ₉ SO ₃ K) and 18-crown-6-ether was 50 mol% based on the amount shown in Table 1 (based on potassium nonafluorobutanesulfonate). The procedure was the same as in Example 1, except that The evaluation results are shown in Table 1.

Example 4
The same procedure as in Example 1 was conducted except that the amount of 18-crown-6-ether in Example 1 was changed to the amount shown in Table 1 (corresponding to 50 mol% with respect to potassium nonafluorobutanesulfonate). . The evaluation results are shown in Table 1.

(Example 5)
In Example 1, the amount (potassium trifluoromethanesulfonate described amounts listed in Table 1 of potassium trifluoromethanesulfonate, the amount of 18-crown-6-ether in Table 1 in place of potassium nonafluorobutanesulfonate The same procedure as in Example 1 was performed except that an equimolar amount) was used. The evaluation results are shown in Table 1.

(Comparative Examples 1-4)
In Example 1, the same operation as in Example 1 was performed except that 18-crown-6-ether was not used and the amount of the sulfonic acid metal salt was changed to the amount shown in Table 2.
The evaluation results are shown in Table 2.

(Examples 6-8, Comparative Examples 5-7)
In Example 1, the amount of polycarbonate resin used is 80 parts by mass, the amount of glass fiber used is 20 parts by mass, and potassium nonafluorobutanesulfonate, potassium trifluoromethanesulfonate, and 18-crown-6-ether are shown in Table 3. It was carried out in the same manner as in Example 1 except that the amount was as described, and side feed was performed at a speed of 24.1 kg / hr based on the flaky raw material and at a speed of 6.0 kg / hr for glass fiber.
The evaluation results are shown in Table 3.

(Examples 9 to 11, Comparative Examples 8 to 10)
In Example 1, the amount of polycarbonate resin used is 90 parts by mass, the amount of glass fiber used is 10 parts by mass, and potassium nonafluorobutanesulfonate, potassium trifluoromethanesulfonate, and 18-crown-6-ether are shown in Table 4. It was carried out in the same manner as in Example 1 except that the amount was as described, side feed was performed at a speed of 27.1 kg / hr with the flaky raw material at the base, and glass fiber was fed at a speed of 3.0 kg / hr.
The evaluation results are shown in Table 4.

(Examples 12 to 16, Comparative Example 11)
Example 1 was carried out except that polytetrafluoroethylene resin was not used and potassium nonafluorobutanesulfonate, potassium trifluoromethanesulfonate, and 18-crown-6-ether were used in the amounts shown in Table 5. Performed as in Example 1.
The evaluation results are shown in Table 5.

As is apparent from the above tables, the glass fiber reinforced polycarbonate resin composition containing the organic sulfonic acid metal salt (B) and the compound (C) having inclusion ability is excellent in flame retardancy, maximum tensile strength, tensile strength It turns out that it is excellent in an elasticity modulus, bending strength, and a bending elastic modulus.
On the other hand, in the comparative example not containing the compound (C) having inclusion ability, although the flame retardancy is the same level, the tensile maximum strength, tensile elastic modulus, bending strength, bending elastic modulus are compared with those of the examples. I can see that it is inferior.

  The flame-retardant polycarbonate resin composition of the present invention is excellent in flame retardancy and excellent in rigidity and strength. Therefore, it can be used very suitably for various polycarbonate resin molded products that require high flame retardancy and strength, and there are some industrial applications that are extremely high.

Claims (5)

Perfluoroalkanesulfonic acid alkali metal salt (B) 0.01-2 parts by mass , crown ether compound (C) 0.01-2 parts by mass and glass fiber (E) 3 with respect to 100 parts by mass of polycarbonate resin (A) A flame retardant polycarbonate resin composition comprising ˜80 parts by mass . 2. The inclusion complex (D) is formed by inclusion of at least a part of the alkali metal perfluoroalkanesulfonate (B) and at least a part of the crown ether compound (C). The flame-retardant polycarbonate resin composition as described. To polycarbonate resin (A) 100 parts by mass of the flame retardant polycarbonate resin composition according to claim 1 or 2, characterized in that it further comprises from 0.001 to 1 mass parts fluoropolymer (F). Alkali metal perfluoroalkane sulfonate alkali metal salt, K, Na, flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, characterized in that a Cs or Li. Molded article obtained by molding the polycarbonate resin composition according to any one of claims 1-4.