JP4316326B2 - Flame retardant for aromatic polycarbonate resin - Google Patents

Description

  The present invention relates to a flame retardant for a non-bromine / non-phosphorus aromatic polycarbonate resin that can be made flame retardant without reducing the melt stability and heat resistance of the aromatic polycarbonate.

Aromatic polycarbonate is a resin material with excellent mechanical properties such as impact resistance and heat resistance, so it can be used in housing materials and chassis materials for computers, notebook computers, printers, mobile phones, copiers, etc. Alternatively, it is widely used as an electrical / electronic component material.
Aromatic polycarbonate used for OA equipment and electrical / electronic equipment is often required to have flame retardancy at the same time, and at present, aromatic polycarbonate-based materials flame-retardant with phosphorus-based flame retardants are often used. .
However, aromatic polycarbonate materials that use phosphorus flame retardants have the disadvantages that the melt stability of the aromatic polycarbonate is reduced and the heat resistance of the material is greatly reduced. It was damaged.

In consideration of the environment, a flame retardant aromatic polycarbonate resin composition that does not use a brominated flame retardant or a phosphorus flame retardant is demanded.
Under such circumstances, attempts have been made to use silicone compounds as flame retardants for aromatic polycarbonates, but the thermal stability of the silicone compounds themselves is insufficient, which limits the temperature range of the molding process. There was a problem that when the molecular weight of the base polymer was lowered in order to obtain high melt fluidity, the flame retardant effect was not sufficiently exhibited.
In addition, for aromatic polycarbonate, there is a technology that uses an organic sulfonic acid alkali metal salt as a flame retardant, but the amount of the organic sulfonic acid alkali metal salt increases when high flame retardancy is exhibited. However, there is a problem that the melt stability of the resin is insufficient.

  An object of the present invention is to provide a flame retardant for a non-bromine / non-phosphorus aromatic polycarbonate resin that can be made flame retardant without reducing the melt stability and heat resistance of the aromatic polycarbonate.

As a result of intensive studies on the above problems, the use of a silicate compound carrying an organic sulfonic acid compound and / or an organic sulfonic acid compound derivative as a flame retardant for an aromatic polycarbonate has improved melt stability and heat resistance. The present inventors have found the surprising fact that an aromatic polycarbonate can be effectively flame retardant without impairing the above, and have reached the present invention.
That is, the present invention includes the following [1] to [4].
[1] A flame retardant for an aromatic polycarbonate resin, wherein an organic sulfonic acid compound and / or an organic sulfonic acid compound derivative (B) is supported on the silicate compound (A).

[2] The flame retardant for aromatic polycarbonate resin has a pH value measured in accordance with JIS K5101 in a range of 4.0 to 8.0 after heat treatment for 1 hour in a temperature environment of 200 ° C. The flame retardant for an aromatic polycarbonate resin according to the above [1].
[3] The flame retardant for an aromatic polycarbonate resin according to [1] or [2], wherein the silicate compound (A) is at least one selected from talc and mica.
[4] With respect to 100 parts by weight of the flame retardant for aromatic polycarbonate resin, 0.001 to 10 parts by weight of at least one metal salt (C) selected from organic alkali metal salts and organic alkaline earth metal salts The flame retardant for aromatic polycarbonate resin according to any one of the above [1] to [3] , comprising:

  The resin composition flame-retarded by using the flame retardant for aromatic polycarbonate resin of the present invention is (1) a non-bromine / non-phosphorus flame-retardant resin material, and has a low environmental load. (2) Excellent melt stability enables molding at high melt resin temperature, excellent molding processability, and (3) excellent heat resistance and mechanical properties inherent in aromatic polycarbonates. The flame retardant for aromatic polycarbonate resin of the present invention is extremely useful industrially.

The present invention will be specifically described below.
Silicate compound used in the flame retardant (A) of the present invention is a silicate compound comprising a metal oxide component and SiO ₂ component. The silicate compound of component (A) may be in any form such as orthosilicate, disilicate, cyclic silicate, chain silicate, layered silicate, etc.
The component (A) may be any compound of complex oxide, oxyacid salt, and solid solution, and the complex oxide may be a combination of two or more of a single oxide and 2 of a single oxide and an oxyacid salt. The solid solution may be either a solid solution of two or more metal oxides or a solid solution of two or more oxyacid salts.

The component (A) may be a hydrate. The form of crystal water in the hydrate is contained as hydrogen silicate ion as Si—OH, contained ionically as hydroxide ion (OH ⁻ ) with respect to metal cation, and contained as water molecule in the gap of structure Any of these may be used.
In addition, as the component (A), both natural products and artificial synthetic products can be used. As the artificial compound, silicate compounds obtained from various conventionally known methods, for example, various synthesis methods using a solid reaction, a hydrothermal reaction, an ultrahigh pressure reaction, and the like can be used.
The silicate compound of component (A) preferably has a composition substantially represented by the following formula (1).
xMO.ySiO ₂ .zH ₂ O (1)
(Here, x and y represent natural numbers, z represents an integer of 0 or more, MO represents a metal oxide component, and may be a plurality of metal oxide components.)

Examples of the metal M in the metal oxide MO include potassium, sodium, lithium, barium, calcium, zinc, manganese, iron, cobalt, magnesium, zirconium, aluminum, and titanium.
In the metal oxide MO, preferred is one that substantially contains either CaO or MgO. Further preferred is the case where the metal oxide MO consists essentially of at least one component selected from CaO and MgO, and particularly preferred is the case consisting essentially of MgO.

Specific examples of the component (A) include talc, mica, wollastonite, zonotlite, kaolin clay, montmorillonite, bentonite, sepiolite, imogolite, sericite, lawsonite, smectite, glass fiber, glass flake, glass beads, and the like. be able to.
In addition, the component (A) can be of any shape (plate, needle, granular, fibrous, etc.), and among these, the one in the form of a plate is the most as the component (A) of the present invention. It can be preferably used.
The average particle size of the component (A) is preferably 0.001 to 500 μm, more preferably 0.01 to 100 μm, still more preferably 0.1 to 50 μm, and particularly preferably 1 to 30 μm.

In addition, the average particle diameter as used in the field of this invention is measured using the following method with the distribution range of the approximate particle diameter of a component (A), and the kind of component (A).
When the particle diameter of the component (A) is distributed in a range of approximately 0.001 to 0.1 μm, an observation photograph of a transmission electron microscope is taken, and the area S of the particles is obtained for 100 or more particles. Using S, (4S / π) ^0.5 is determined as the particle diameter of each particle, and the number average particle diameter is determined.
When the particle diameter of the component (A) is distributed in the range of about 0.1 to 300 μm, the average particle diameter is determined by a laser diffraction method (for example, using SALD-2000 manufactured by Shimadzu Corporation).
When the component (A) is any one of glass fiber, glass flake, and glass bead, it is calculated as the median diameter of the particle size distribution obtained by the standard sieving method.

As the component (A) of the present invention, talc and mica are particularly preferable.
The talc that can be preferably used as the component (A) of the present invention is a hydrous magnesium silicate having a layered structure, represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O, usually about 63 wt% SiO _2, about MgO about It contains 32%, H ₂ O about 5% by weight, Fe ₂ O ₃ , CaO, Al ₂ O _{3 and the} like, and the specific gravity is about 2.7.
Moreover, as the talc that can be used as the component (A) of the present invention, calcined talc, talc that is washed with hydrochloric acid to remove impurities, and the like can be preferably used. Furthermore, talc that has been subjected to surface hydrophobic treatment with a silane coupling agent, a titanate coupling agent, or the like can also be used.

On the other hand, mica that can be preferably used as the component (A) of the present invention is a pulverized product of a silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, artificial mica and the like. Any mica can be used as the mica of the present invention, but muscovite is preferred.
Such mica may be subjected to surface hydrophobic treatment with a silane coupling agent, a titanate coupling agent, or the like.
Component (B) used in the flame retardant of the present invention is an organic sulfonic acid compound and / or an organic sulfonic acid compound derivative.

The “organic sulfonic acid compound” represents an organic compound containing at least one —SO ₃ H group in the molecular structure, and the “organic sulfonic acid compound derivative” is derived from the organic sulfonic acid compound. Sulfonic acid ester, sulfonic acid ammonium salt, sulfonic acid phosphonium salt, and the like.
In the present invention, the component (B) can be not only a low molecular compound but also an oligomer or polymer.
As the organic sulfonic acid compound that can be preferably used as the component (B) of the present invention, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, diisobutylnaphthalenesulfonic acid, dodecyl Examples include aromatic sulfonic acids such as benzenesulfonic acid, aliphatic sulfonic acids having 8 to 18 carbon atoms, sulfonated polystyrene, polymers such as methyl acrylate / sulfonated styrene copolymer, and oligomeric organic sulfonic acids. be able to.

  Among the organic sulfonic acid compound derivatives that can be used as the component (B) of the present invention, sulfonic acid esters that can be preferably used include methyl benzenesulfonate, ethyl benzenesulfonate, propyl benzenesulfonate, and benzenesulfonic acid. Butyl, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, p-toluene Phenyl sulfonate, methyl naphthalene sulfonate, ethyl naphthalene sulfonate, propyl naphthalene sulfonate, butyl naphthalene sulfonate, 2-phenyl-2-propyl dodecyl benzene sulfonate, dodecyl benzene sulfate Phosphate-2-phenyl-2-butyl, and the like.

  Among the organic sulfonic acid compound derivatives that can be used as the component (B) of the present invention, sulfonic acid ammonium salts that can be preferably used include decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, and dodecyl ammonium. Ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate, decyl trimethyl ammonium hexadecyl sulfate, tetrabutyl ammonium dodecyl benzyl sulfate, tetraethyl ammonium dodecyl benzyl sulfate, tetra Methylan Um dodecylbenzyl sulfate, and the like.

Further, among the organic sulfonic acid compound derivatives that can be used as the component (B) of the present invention, sulfonic acid boronic acid salts that can be preferably used include octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzene Examples thereof include tetrabutylphosphonium sulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, and the like.
In the present invention, the component (B) is not limited to the compounds exemplified above, and two or more kinds can be used in combination.

Furthermore, the component (B) may be an organic sulfonic acid compound containing —OH 3 group, —NH ₂ group, —COOH group, halogen group, etc. in addition to —SO ₃ H group in the molecular structure. Naphthol sulfonic acid, sulfamyl acid, naphthylamine sulfonic acid, sulfobenzoic acid, fully substituted or partially substituted chloro group-containing organic sulfonic acid, fully substituted or partially substituted fluoro group-containing organic sulfonic acid, and the like.
Among the components (B) that can be used in the flame retardant of the present invention, an aromatic sulfonic acid compound can be particularly preferably used. For example, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. Particularly preferred.

The flame retardant for aromatic polycarbonate resin of the present invention carries an organic sulfonic acid compound and / or an organic sulfonic acid compound derivative (B) with respect to the silicate compound (A).
Here, “supported” means that the organic sulfonic acid compound and / or the organic sulfonic acid compound derivative (B) is bonded to the surface and inside of the silicate compound (A) with a covalent bond, an ionic bond, a hydrogen bond, and Represents the overall state carried by any of the van der Waals forces.
In the flame retardant for aromatic polycarbonate resin of the present invention, the component (B) may be supported in layers on the surface and inside of the component (A) or may be partially supported.

Examples of the method for obtaining the flame retardant for aromatic polycarbonate resin of the present invention include the following methods (1) to (4).
(1) A predetermined amount of the organic sulfonic acid compound and / or the organic sulfonic acid compound derivative (B) is blended with the silicate compound (A), and a mechanical mixing device such as a Henschel mixer, a Nauta mixer, a V blender, or a tumbler. A method of mixing and stirring using
(2) An organic sulfonic acid compound and / or an organic sulfonic acid compound derivative (B) diluted with a solvent is brought into contact with the silicate compound (A) by a method such as spraying, dripping, wetting or dipping, and Henschel A method in which a mixing and stirring process is performed using a mechanical mixing device such as a mixer, a nauta mixer, a V blender, or a tumbler, and then the solvent is devolatilized and dried. In this case, water, an organic solvent, a water / organic solvent mixed solvent, or an organic solvent / organic solvent mixed solvent can be used as the solvent.

(3) The organic sulfonic acid compound and / or the organic sulfonic acid compound derivative (B) is sprayed or dropped into contact with the silicate compound (A) in a liquid state, such as a Henschel mixer, a Nauta mixer, a V blender, or a tumbler. A method of mixing and stirring using a mechanical mixing device. In this case, in order to make a component (B) into a liquid state, it can also heat as needed.
(4) The organic sulfonic acid compound and / or the organic sulfonic acid compound derivative (B) is heated and brought into contact with the silicate compound (A) in a gas state, and if necessary, a Henschel mixer, a Nauta mixer, a V blender, A method of mixing and stirring using a mechanical mixer such as a tumbler. In this case, in order to make this organic acidic compound and / or organic acidic compound derivative into a gaseous state, it can also be heated as needed.

As a method for obtaining the flame retardant for an aromatic polycarbonate resin of the present invention, the above methods (1) to (4) may be combined.
Among the methods exemplified in the above (1) to (4), the method (3) or (4) is particularly preferable from the viewpoints of the completeness of the treatment and the simplicity of the work process.
In the flame retardant for aromatic polycarbonate resin of the present invention, the blending ratio of component (B) to component (A) depends on the type of component (A) used, but is usually based on 100 weight of component (A). 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight.

In addition, the flame retardant for aromatic polycarbonate resin of the present invention has a pH value of 4 measured according to JIS K5101 after heat-treating the flame retardant for aromatic polycarbonate resin in a temperature environment of 200 ° C. for 1 hour. It is preferably in the range of 0.0 to 8.0, more preferably in the range of 4.5 to 7.5, still more preferably in the range of 5.0 to 7.2. A range of 7.0 is particularly preferred.
The flame retardant for an aromatic polycarbonate resin of the present invention having a pH value measured after carrying out a heat treatment for 1 hour in a temperature environment of 200 ° C. is within the above range, the component (A) constituting the flame retardant This indicates that the component (B) is thermally and strongly supported and that the excess component (B) is not contained. For this reason, the melt stability of the aromatic polycarbonate is indicated. And flame retardancy can be enhanced at the same time.
The aromatic polycarbonate resin in which the flame retardant of the present invention can be used is an aromatic polycarbonate or a resin mainly composed of an aromatic polycarbonate.
Here, the resin mainly composed of an aromatic polycarbonate represents a component in which the component exceeding 50% by weight of the resin component is an aromatic polycarbonate and the remaining resin component is a thermoplastic resin other than the aromatic polycarbonate.

  The aromatic polycarbonate preferably used as the aromatic polycarbonate resin in which the flame retardant of the present invention can be used is an aromatic polycarbonate derived from an aromatic dihydroxy compound. Examples of the aromatic dihydroxy compound include 1,1 -Bis (4-hydroxy-t-butylphenyl) propane, bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, dihydroxyaryls such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether Ethers 4,4 -Dihydroxydiphenyl sulfide, dihydroxyaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethylphenyl Examples thereof include dihydroxyaryl sulfoxides such as sulfoxide, dihydroxyaryl sulfones such as 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethylphenylsulfone, and the like.

Among these, 2,2-bis (4-hydroxyphenyl) propane (common name, bisphenol A) is particularly preferable. These aromatic dihydroxy compounds can be used alone or in combination of two or more.
What was manufactured by the well-known method can be used for the said aromatic polycarbonate. Specifically, a known method of reacting an aromatic dihydroxy compound and a carbonate precursor, for example, reacting an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. Crystallized carbonate prepolymer obtained by interfacial polymerization method (eg phosgene method), transesterification method (melting method) in which aromatic dihydroxy compound and carbonic acid diester (eg diphenyl carbonate) are reacted, phosgene method or melting method Polymerization methods (Japanese Patent Laid-Open No. 1-158033 (corresponding to US Pat. No. 4,948,871), Japanese Patent Laid-Open No. 1-271426, Japanese Patent Laid-Open No. 3-68627 (corresponding to US Pat. No. 5,204,377)), etc. What was manufactured by the method can be used.

Particularly preferred as the aromatic polycarbonate resin in which the flame retardant of the present invention can be used contains substantially a chlorine atom produced by a transesterification method from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester. There is no aromatic polycarbonate.
The weight average molecular weight (Mw) of the aromatic polycarbonate is usually 5,000 to 500,000, preferably 10,000 to 100,000, more preferably 13,000 to 50,000, still more preferably. It is 14,000 to 30,000, particularly preferably 15,000 to 25,000, and most preferably 16,000 to 23,000.

In the present invention, the weight average molecular weight (Mw) of the aromatic polycarbonate can be measured using gel permeation chromatography (GPC), and the measurement conditions are as follows. That is, it is obtained by using a converted molecular weight calibration curve according to the following formula from the composition curve of standard monodisperse polystyrene using polystyrene gel with tetrahydrofuran as a solvent.
M _PC = 0.3591 M _PS ^1.0388
( _MPC is the molecular weight of aromatic polycarbonate, _MPS is the molecular weight of polystyrene)
In the present invention, the aromatic polycarbonate may be used in combination of two or more aromatic polycarbonates having different molecular weights. For example, an aromatic polycarbonate of an optical disk material whose Mw is usually in the range of 14,000 to 16,000, and an aromatic polycarbonate for injection molding or extrusion molding whose Mw is usually in the range of 20,000 to 50,000. Can also be used in combination.

  Examples of the thermoplastic resin other than the aromatic polycarbonate that can be preferably used in the resin mainly composed of the aromatic polycarbonate include polystyrene, high impact polystyrene (HIPS), acrylonitrile / styrene resin (AS resin), and butyl acrylate.・ Acrylonitrile styrene resin (BAAS resin), acrylonitrile butadiene styrene resin (ABS resin), methyl methacrylate butadiene styrene resin (MBS resin), butyl acrylate acrylonitrile styrene resin (AAS resin), polyethylene terephthalate and polybutylene Examples thereof include polyester resins such as terephthalate, polyamide resins, polymethyl methacrylate, polyarylate, and other thermoplastic resins. In particular, AS resin and BAAS resin are preferable for improving fluidity, ABS resin and MBS resin are preferable for improving impact resistance, and polyester resin is preferable for improving chemical resistance.

In the resin mainly composed of the polycarbonate, the content of the thermoplastic resin other than the aromatic polycarbonate is preferably 0.1 to 30% by weight of the resin component, more preferably 0.5 to 20 parts by weight, and 1 to 15 parts by weight. Is more preferable.
The amount of the flame retardant for aromatic polycarbonate resin of the present invention is usually in the range of 0.01 to 200 parts by weight, preferably 0.1 to 100 parts by weight, with respect to 100 parts by weight of the aromatic polycarbonate resin. 0.5-50 weight part is more preferable, 1-30 weight part is still more preferable, and 3-20 weight part is the most preferable.
The flame retardant for aromatic polycarbonate resin of the present invention is further provided with at least one metal salt selected from an organic alkali metal salt and an organic alkaline earth metal salt with respect to 100 parts by weight of the flame retardant for aromatic polycarbonate resin ( C) By including 0.001-10 weight part, it can be set as the flame retardant for aromatic polycarbonate resin which the effect as a flame retardant was further excellent.

In the present invention, a metal salt of an organic sulfonic acid and / or a metal salt of a sulfate ester is preferably used as at least one metal salt (C) selected from an organic alkali metal salt and an organic alkaline earth metal salt. Can do. Moreover, these can be used not only independently but in mixture of 2 or more types. The alkali metal of the present invention includes lithium, sodium, potassium, rubidium and cesium, and the alkaline earth metal includes beryllium, magnesium, calcium, strontium and barium, particularly preferably lithium, sodium, Potassium.
Examples of the metal salt of the organic sulfonic acid that can be preferably used in the present invention include aliphatic sulfonate alkali (earth) metal salts and aromatic sulfonate alkali (earth) metal salts. In the present specification, the expression “alkali (earth) metal salt” is used to mean both alkali metal salts and alkaline earth metal salts.

As the aliphatic (alkali earth) metal salt of an aliphatic sulfonate, an alkane sulfonic acid alkali (earth) metal salt having 1 to 8 carbon atoms or a part of the alkyl group of the alkane sulfonic acid alkali (earth) metal salt includes Alkali (earth) metal sulfonates substituted with fluorine atoms, and alkali (earth) metal perfluoroalkane sulfonates having 1 to 8 carbon atoms can be preferably used. Fluoroethanesulfonic acid sodium salt and perfluorobutanesulfonic acid potassium salt can be mentioned.
In addition, as the aromatic (earth) metal salt of an aromatic sulfonate, as an aromatic sulfonic acid, a monomeric or polymeric aromatic sulfide sulfonic acid, an aromatic carboxylic acid and an ester sulfonic acid, a monomeric or polymeric form Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid And aromatic sulfonic acid alkali (earth) metal salts in which at least one selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids is used as an aromatic sulfonic acid Can do.

Preferred examples of the above-mentioned monomeric or polymeric aromatic sulfonic acid alkali (earth) metal salts include diphenyl sulfide-4,4′-disulfonic acid disodium, diphenyl sulfide-4,4′-disulfone. Mention may be made of dipotassium acid.
Preferred examples of the sulfonic acid alkali (earth) metal salt of the aromatic carboxylic acid and ester include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate. Can do.

  In addition, preferable examples of the monomeric or polymeric aromatic ether sulfonate alkali (earth) metal salts include calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, Poly (2,6-dimethylphenylene oxide) polysodium sulfonate, poly (1,3-phenylene oxide) polysodium sulfonate, poly (1,4-phenylene oxide) polysodium sulfonate, poly (2,6-diphenyl) Phenylene oxide) polypotassium polysulfonate, lithium poly (2-fluoro-6-butylphenylene oxide) polysulfonate.

Moreover, the sulfonic-acid alkali (earth) metal salt of the said aromatic sulfonate can mention the potassium sulfonate of benzenesulfonate as the preferable example.
The monomeric or polymeric aromatic (earth) metal sulfonates are preferably sodium benzenesulfonate, potassium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, p-benzene. Examples include dipotassium disulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3′-disulfonate, sodium toluenesulfonate, potassium toluenesulfonate, and potassium xylenesulfonate.

The monomeric or polymeric aromatic sulfonesulfonic acid alkali (earth) metal salts include, as preferred examples, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, and diphenylsulfone-3. , 3′-disulfonic acid dipotassium, diphenylsulfone-3,4′-disulfonic acid dipotassium.
Preferred examples of the above-mentioned aromatic sulfonate alkali (earth) metal salts of aromatic ketones include sodium α, α, α-trifluoroacetophenone-4-sulfonate and dipotassium benzophenone-3,3′-disulfonate. Can do.

Preferred examples of the above-mentioned alkali sulfonic acid alkali (earth) metal salt include disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, and calcium thiophene-2,5-disulfonate. And sodium benzothiophene sulfonate.
As a preferable example of the sulfonic acid alkali (earth) metal salt of the aromatic sulfoxide, potassium diphenyl sulfoxide-4-sulfonate can be mentioned.
Preferable examples of the condensate obtained by methylene bond of the alkali (earth) metal salt of aromatic sulfonate include a formalin condensate of sodium naphthalene sulfonate and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, as the alkali (earth) metal salt of a sulfate ester, a monovalent and / or alkali (earth) metal salt of a sulfate ester of a polyhydric alcohol can be preferably used in the present invention. As sulfates of polyhydric alcohols, methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate And sulfuric acid ester of lauric acid monoglyceride, sulfuric acid ester of palmitic acid monoglyceride, and sulfuric acid ester of stearic acid monoglyceride. Particularly preferable examples of the alkali (earth) metal salts of these sulfates include the alkali (earth) metal salts of lauryl sulfate.

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, Examples thereof include N- (N′-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.
Among the components (C) listed above, more preferable alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonic acid and alkali (earth) metal salts of perfluoroalkanesulfonic acid. Can be mentioned.

In the flame retardant for aromatic polycarbonate resin of the present invention, when the component (C) is used, the amount used is 0.01 to 8 parts by weight with respect to 100 parts by weight of the flame retardant for aromatic polycarbonate resin. More preferably, 0.1-5 weight part is further more preferable, and 0.5-3 weight part is especially preferable.
Moreover, in the flame-retardant aromatic polycarbonate resin composition which uses the flame retardant for aromatic polycarbonate resin of this invention, a fluoropolymer can be included as a dripping agent of a combustion thing. In this case, it is preferable to use a fluoropolymer having a fibril-forming ability as the fluoropolymer, and examples thereof include tetrafluoroethylene polymers such as polytetrafluoroethylene and tetrafluoroethylene / propylene copolymers.

  As the fluoropolymer, various forms of fluoropolymer such as a fine powder fluoropolymer, an aqueous dispersion of fluoropolymer, and a powdery mixture with a second resin such as AS or PMMA can be used. Aqueous dispersions of fluoropolymers include “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon D-1”, “Polyflon D-2”, “Polyflon D-” manufactured by Daikin Industries, Ltd. 2C "and" Polyflon D-2CE ". Further, as a fluoropolymer in a powdery mixture with a second resin such as AS or PMMA, “Blendex 449” manufactured by GE Specialty Chemicals and “Metabrene A-3800” manufactured by Mitsubishi Rayon Co., Ltd. may be exemplified. it can.

In the flame retardant aromatic polycarbonate resin composition using the flame retardant for aromatic polycarbonate resin of the present invention, when the fluoropolymer is used, the amount used is 0.01 with respect to 100 parts by weight of the aromatic polycarbonate resin. -5 parts by weight is preferred, 0.03-3 parts by weight is more preferred, 0.05-1 part by weight is still more preferred, and 0.1-0.5 part by weight is particularly preferred.
In the flame retardant aromatic polycarbonate resin composition using the flame retardant for aromatic polycarbonate resin of the present invention, if necessary, further, a colorant, a lubricant, a release agent, a heat stabilizer, an antioxidant, an ultraviolet ray Absorbers, antistatic agents and the like can also be added.

Next, the manufacturing method of the flame-retardant aromatic polycarbonate resin composition which uses the flame retardant for aromatic polycarbonate resins of this invention is demonstrated.
In order to mix the flame retardant for aromatic polycarbonate resin of the present invention with the aromatic polycarbonate resin, it is preferable to melt and knead it using a melt kneading apparatus such as an extruder.
In performing melt-kneading, generally used apparatuses such as premixing apparatuses such as a tumbler and ribbon blender, and melt-kneading apparatuses such as a single screw extruder, a twin screw extruder, and a kneader can be used. The raw materials can be supplied to the melt-kneading apparatus after preliminarily mixing each component, but each component can also be supplied independently to the melt-kneading apparatus.

As the melt-kneading apparatus, an extruder, preferably a twin-screw extruder can be used.
The melt-kneading is usually carried out by appropriately selecting the cylinder set temperature of the extruder at 200 to 300 ° C, preferably 220 to 270 ° C, and the extruder screw speed of 100 to 700 rpm, preferably 200 to 500 rpm. However, care should be taken not to give excessive heat during melt-kneading. Furthermore, if necessary, it is also effective to provide an opening (vent port) in the latter part of the extruder and perform open devolatilization or vacuum devolatilization. Further, the residence time of the raw material resin in the extruder is usually selected appropriately within a range of 10 to 60 seconds.
The method for molding the flame retardant aromatic aromatic polycarbonate resin composition obtained using the flame retardant for aromatic polycarbonate resin of the present invention is not particularly limited, and examples thereof include injection molding, gas assist molding, extrusion molding, and compression. Among them, injection molding and extrusion molding are preferably used, and injection molding is particularly preferably used.

  Examples of molded products using the flame retardant aromatic aromatic polycarbonate resin composition obtained by using the flame retardant for aromatic polycarbonate resin of the present invention include computers, notebook computers, copying machines, printers, and liquid crystal projectors. , Housing materials for electric / electronic devices, mobile phones, personal digital assistants, battery packs, home appliances, frame materials for LCD backlights, parts for copier internal parts, resistors, terminals, deflection yokes for TVs And other electrical / electronic component materials, lighting component materials, flame retardant sheets (insulating sheets) for electronic / information devices, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The following components (A), (B), and optionally (C) were used to prepare flame retardants for aromatic polycarbonate resins.
1. Component (A): Silicate compound (A-1)
Talc with an average particle size of 5 μm, a bulk specific volume of 2.3 cm ³ / g, a water content of 0.2 wt%, and a pH of 9.0 (trade name “Microace P3” manufactured by Nippon Talc Co., Ltd.)
(A-2)
Mica having a weight average flake diameter of 90 μm, a weight average aspect ratio of 50, and a bulk specific gravity of 0.27 g / cm ³ (trade name “Kuralite Mica 200-D” manufactured by Kuraray Co., Ltd.)

2. Component (B): Organic sulfonic acid compound and / or organic sulfonic acid compound derivative (B-1)
p-Toluenesulfonic acid (Wako Pure Chemical Industries, Ltd.)
(B-2)
p-Toluenesulfonate methyl (Wako Pure Chemical Industries, Ltd.)
3. Component (C): At least one metal salt selected from organic alkali metal salts and organic alkaline earth metal salts (C-1)
Perfluorobutanesulfonic acid potassium salt (trade name “F-top KFBS” manufactured by Mitsubishi Materials Corporation)

[Preparation of flame retardant for aromatic polycarbonate resin (flame retardant 1)]
30 kg of talc (A-1) and 1 kg of p-toluenesulfonic acid (B-1) were put into a 100 liter Nauta mixer with a jacket temperature of 200 ° C., screw shaft rotation speed 90 rpm, screw circumference Stirring was performed for 2 hours at a stirring speed of 3 rpm. The temperature of the powder during the stirring process reached about 165 ° C. After stirring for 2 hours, the inside of the Nauta mixer was depressurized (0.01 MPa), and stirring was continued for another 30 minutes. Thereafter, the treated powder was discharged from the mixer to obtain a flame retardant for aromatic polycarbonate resin (flame retardant 1). When this (flame retardant 1) was left in an oven set at 200 ° C. for 1 hour and then cooled to room temperature, the pH value was measured according to JIS K5101 to be 6.5.

[Preparation of flame retardant for aromatic polycarbonate resin (flame retardant 2)]
1 kg of mica (A-2) and 10 g of methyl p-toluenesulfonate (B-2) were put into a 10 liter Henschel mixer, and stirred for 10 minutes at a screw shaft speed of 1,450 rpm. Thereafter, the treated powder was discharged from the mixer to obtain a flame retardant for aromatic polycarbonate resin (flame retardant 2). When this (flame retardant 2) was left in an oven set at 200 ° C. for 1 hour and then cooled to room temperature, the pH value measured according to JIS K5101 was 7.2.

[Preparation of flame retardant for aromatic polycarbonate resin (flame retardant 3)]
1 kg of talc (A-1), 30 g of p-toluenesulfonic acid (B-1), and 10 g of perfluorobutanesulfonic acid potassium salt (C-1) are put into a 10 liter Henschel mixer, and the screw shaft is rotated. The stirring treatment was performed at several 1,450 rpm for 10 minutes. Thereafter, the treated powder was discharged from the mixer to obtain a flame retardant for aromatic polycarbonate resin (flame retardant 3). The (flame retardant 3) was left in an oven set at 200 ° C. for 1 hour, then cooled to room temperature, and then the pH value was measured according to JIS K5101.
Table 1 shows the composition of flame retardants 1 to 3 for aromatic polycarbonate resin.

The present invention will be described based on examples.
[Examples 1 to 4 and Comparative Examples 1 to 4]
Using the flame retardant for aromatic polycarbonate resin (flame retardants 1 to 3) prepared by the method described above and the following raw materials, the amount shown in Table 2 (unit: parts by weight) was melted using a twin screw extruder. A polycarbonate flame retardant resin composition was obtained by kneading.
(Aromatic polycarbonate)
A bisphenol A polycarbonate produced by melt transesterification from bisphenol A and diphenyl carbonate and having a weight average molecular weight of 20,500 (indicated as “PC” in Table 2)

(Fluoropolymer)
50/50 (weight ratio) powdery mixture of polytetrafluoroethylene (PTFE) and acrylonitrile / styrene copolymer (AS) (trade name “Blendex 449” manufactured by GE Specialty Chemicals) (“PTFE / AS” in Table 2) Expressed as)
(Release agent)
Pentaerythritol tetrastearate (trade name “Unistar H476” manufactured by NOF Corporation) (represented as “PETS” in Table 2)
Using a twin-screw extruder (ZSK-25, L / D = 37, manufactured by Werner & Pfleiderer) as a melt-kneading device, a cylinder set temperature of 250 ° C., a screw rotation speed of 200 rpm, and a kneading resin discharge speed of 15 kg / Hr. Melt kneading was performed under the conditions.
During melt kneading, the temperature of the molten resin measured by a thermocouple at the extruder die was 260 to 270 ° C.
Raw materials were charged into the twin-screw extruder by pre-blending with a tumbler for 10 minutes using a feeder. In addition, a vent port was provided in the latter part of the extruder to perform open-air devolatilization.

The obtained pellets were dried at 120 ° C. for 5 hours and molded with an injection molding machine, and the following tests were performed.
(1) Measurement of increase rate of melt index (MI) after staying in molding machine Molding a 1/8 inch thick strip with an injection molding machine (Autoshot 50D, manufactured by FANUC) with a cylinder temperature set to 300 ° C. The strips obtained were cut out and the MI value was measured according to ISO 1133 at a furnace temperature of 300 ° C. and a load of 1.2 kg. (MI ₁ )
Separately, a 1/8 inch thick strip was molded in the same manner as above except that the resin composition was melted and retained for 20 minutes inside the cylinder, and the MI value was measured by cutting out the obtained strip. . (MI ₂ )
From the values of MI ₁ and MI ₂ , the MI increase rate was calculated according to the following formula.
MI increase rate = (MI ₂ −MI ₁ ) / MI ₁ × 100

(2) Measurement of deflection temperature under load The deflection temperature under load was measured under a load of 1.82 MPa according to ISO 75-1. The test piece was molded using an injection molding machine (Autoshot 50D, manufactured by FANUC) with the cylinder temperature set at 280 ° C. (Unit: ° C)
(3) Flame retardance A strip-shaped molded product (thickness 1.5 mm and 1.0 mm) for a combustion test was set to a cylinder set temperature of 300 ° C. and a mold set by an injection molding machine (Autoshot 100D, manufactured by FANUC). Molding was performed at a temperature of 80 ° C. and maintained for 2 days in an environment of a temperature of 23 ° C. and a humidity of 50%. Then, a 20 mm vertical combustion test was conducted according to the UL-94 standard, and V-0, V-1, V-2. , NC (NC is non-classification).
The results are shown in Table 2.

  The flame retardant for aromatic polycarbonate resin of the present invention is a non-bromine / non-phosphorus low environmental load type aromatic polycarbonate resin that can be flame retardant without reducing melt stability and heat resistance. It is a flame retardant and is extremely useful industrially.

Claims (4)

  A flame retardant for an aromatic polycarbonate resin, wherein an organic sulfonic acid compound and / or an organic sulfonic acid compound derivative (B) is supported on the silicate compound (A).   The flame retardant for aromatic polycarbonate resin has a pH value measured in accordance with JIS K5101 in a range of 4.0 to 8.0 after heat treatment for 1 hour in a temperature environment of 200 ° C. The flame retardant for aromatic polycarbonate resin according to claim 1. The flame retardant for an aromatic polycarbonate resin according to claim 1 or 2, wherein the silicate compound (A) is at least one selected from talc and mica.
Further, at least one metal salt (C) 0.00 selected from organic alkali metal salts and organic alkaline earth metal salts is added to 100 parts by weight of the flame retardant for aromatic polycarbonate resin.
The aromatic polycarbonate resin for flame retardant according to any one of claims 1 to 3, characterized in that it comprises 1 to 10 parts by weight.