JP7060452B2 - High-concentration phosphorus flame retardant masterbatch, polycarbonate resin composition, and method for manufacturing masterbatch - Google Patents

Description

The present invention relates to a high-concentration phosphorus-based flame retardant masterbatch, a polycarbonate resin composition, and a method for producing a masterbatch.

Polycarbonate resin is a resin with excellent heat resistance and mechanical properties, so for example, electrical equipment, electronic equipment, vehicles such as automobiles, OA / information equipment such as printers and copiers, housing, construction, and other industries. It is widely used as a material for manufacturing parts in the field. Products such as these resin molded products are required to be flame-retardant from the viewpoint of safety for the purpose of preventing fires due to high temperatures. In particular, flame-retardant polycarbonate resin compositions are used for computers, personal computers, and various mobile terminals. , It is suitably used as a housing for a battery or the like.

Conventionally, as a means for imparting flame retardancy to a polycarbonate resin, a method of blending a halogen-based flame retardant such as an organic bromine compound with the polycarbonate resin is widely known, but a resin in which a halogen-based flame retardant is blended with the polycarbonate resin. The composition may have reduced thermal stability and may cause corrosion of the molding machine screws and molds during the molding process. In addition, if a halogen-based flame retardant is blended, there is a risk that gas containing the halogen will be generated during combustion, and environmental pollution may become a problem during product disposal and recovery. It is required to be burned.

Then, in Patent Document 1, it is proposed to add a phosphorus-based flame retardant to the polycarbonate resin instead of the halogen-based flame retardant, and the phosphorus-based flame retardant is now becoming the main component.

Japanese Unexamined Patent Publication No. 62-4746

Phosphorus-based flame retardants, for example, phosphoric acid ester-based flame retardants, include solid and liquid ones at room temperature, and the liquid ones require liquid addition to the extruder. However, when a liquid phosphorus-based flame retardant and a polycarbonate resin are melt-kneaded using an extruder, an unmelted product of the polycarbonate resin is generated, and it is difficult to achieve uniform dispersion of the phosphorus-based flame retardant. The flame retardancy of the obtained polycarbonate resin composition pellets tends to be insufficient.
An object (problem) of the present invention is to obtain a high-concentration masterbatch of a liquid phosphorus-based flame retardant and use it to obtain a flame-retardant polycarbonate resin composition in view of the above-mentioned problems of the prior art. The purpose is to obtain a high-quality resin composition.

As a result of diligent studies to achieve the above problems, the present inventors compounded the polycarbonate resin and the liquid phosphorus flame retardant so as to have a concentration of 25 to 45% by mass to master the liquid phosphorus flame retardant. The present invention has been completed by finding that a highly flame-retardant resin composition can be obtained by obtaining a batch and using it to obtain a flame-retardant polycarbonate resin composition.

That is, according to the first invention, the polycarbonate resin is 55 to 75% by mass, the phosphorus-based flame retardant liquid at room temperature is 25 to 45% by mass, and the stabilizer is 0 to 0 to 75% by mass based on the total of 100% by mass of the following components. Provided is a high concentration phosphorus flame retardant masterbatch characterized by containing 0.1% by mass.
Further, according to the second invention, the polycarbonate resin is 62 to 75% by mass, the fluorine-containing resin is 0.1 to 1% by mass, and the stabilizer is 0.01 to 0% by mass based on the total of 100% by mass of the following components. Provided is a flame-retardant polycarbonate resin composition comprising 2% by mass and 25 to 38% by mass of the masterbatch according to claim 1.
Further, according to the third invention, the polycarbonate resin is 52 to 73% by mass, the fluorine-containing resin is 0.1 to 1% by mass, and the core-shell type elastomer is 2 to 10% by mass based on the total of 100% by mass of the following components. , A flame-retardant polycarbonate resin composition comprising 0.01 to 0.2% by mass of a stabilizer and 25 to 38% by mass of the master batch according to claim 1.
Further, according to the fourth invention, the polycarbonate resin is supplied to the twin-screw extruder, and after the polycarbonate resin is melted in the kneading portion, the phosphorus-based flame retardant liquid at room temperature is added in an amount of 25 to 45% by mass based on the whole. Provided is a method for producing a high-concentration phosphorus-based flame retardant masterbatch, which comprises melt-kneading a polycarbonate resin and a liquid phosphorus-based flame retardant in a kneading portion downstream of the extruder.

By compounding the polycarbonate resin and the liquid phosphorus flame retardant to a concentration of 25 to 45% by mass to obtain a liquid phosphorus flame retardant masterbatch, and using it to obtain a flame retardant polycarbonate resin composition. A highly flame-retardant resin composition can be obtained. The cause of this is not clear, but by first kneading a liquid phosphorus flame retardant with a certain concentration with the polycarbonate resin, the affinity between the liquid phosphorus flame retardant and the polycarbonate resin is improved, and it becomes uniform at a level close to the molecular level. It is considered that the flame retardancy of the polycarbonate resin composition obtained by mixing and using it for the second compounding is improved.

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not construed as being limited to the embodiments and examples.

The high-concentration phosphorus-based flame retardant masterbatch of the present invention contains 55 to 75% by mass of a polycarbonate resin, 25 to 45% by mass of a phosphorus-based flame retardant liquid at room temperature, and 0 to 0.1% by mass of a stabilizer. It is characterized by that.

[Polycarbonate resin]
As the polycarbonate resin used in the high-concentration phosphorus-based flame retardant masterbatch and the flame-retardant resin composition of the present invention, any conventionally known polycarbonate resin can be used. Examples of the polycarbonate resin include aromatic polycarbonate resin, aliphatic polycarbonate resin, and aromatic-aliphatic polycarbonate resin, and aromatic polycarbonate resin is preferable.

The aromatic polycarbonate resin is a optionally branched aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a phosgene or carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method) can be used. Further, it may be a polycarbonate resin produced by a melting method and produced by adjusting the amount of OH groups of the terminal groups.

Typical examples of aromatic dihydroxy compounds, which are one of the raw materials for aromatic polycarbonate resins, include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-. Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane , 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4' -Dihydroxybiphenyl, 3,3', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) Examples thereof include ether and bis (4-hydroxyphenyl) ketone.
Further, a polyhydric phenol having three or more hydroxy groups in a molecule such as 1,1,1-tris (4-hydroxyphenyl) ethane, 1,3,5-tris (4-hydroxyphenyl) benzene is branched. It can also be used in small amounts as an agent.
Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. These aromatic dihydroxy compounds can be used alone or in combination of two or more.

To obtain a branched aromatic polycarbonate resin, fluoroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris (4,6-tris) 4-Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3,1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 -Polyhydroxy compounds such as tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxyindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichlorousatin, 5-bromuisatin, etc. May be used as a part of the aromatic dihydroxy compound, and the amount used thereof is 0.01 to 10 mol%, preferably 0.1 to 2 mol% with respect to the hydroxy compound.

In polymerization by the transesterification method, a carbonic acid diester is used as a monomer instead of phosgene. Typical examples of the carbonic acid diester include substituted diaryl carbonate typified by diphenyl carbonate, ditril carbonate and the like, and dialkyl carbonate typified by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable.

Further, the above-mentioned carbonic acid diester may be replaced with a dicarboxylic acid or a dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less. Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalic acid and the like. When substituted with such a dicarboxylic acid or a dicarboxylic acid ester, a polyester carbonate is obtained.

When producing a polycarbonate resin by the transesterification method, a catalyst is usually used. The type of catalyst is not limited, but generally, basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferable. These may be used alone or in combination of two or more. In the transesterification method, it is common to inactivate the above polymerization catalyst with a p-toluenesulfonic acid ester or the like.

Preferred polycarbonate resins are aromatic polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane or derived from 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds. Examples thereof include aromatic polycarbonate copolymers. Further, a polymer or oligomer having a siloxane structure can be copolymerized for the purpose of imparting flame retardancy and the like. The polycarbonate resin may be a mixture of two or more kinds of polymers and / or copolymers having different raw materials, and may have a branched structure up to 0.5 mol%.

The content of the terminal hydroxyl group of the polycarbonate resin has a great influence on the thermal stability, the hydrolysis stability, the color tone and the like. In order to have practical physical properties, the terminal hydroxyl group content of the polycarbonate resin is usually 30 to 2000 ppm, preferably 100 to 1500 ppm, more preferably 200 to 1000 ppm, and the seal for adjusting the terminal hydroxyl group content is adjusted. As the terminal agent, p-tert-butylphenol, phenol, cumylphenol, p-long-chain alkyl-substituted phenol and the like can be used.

The amount of residual monomer in the polycarbonate resin is 150 ppm or less, preferably 100 ppm or less, and more preferably 50 ppm or less for the aromatic dihydroxy compound. When synthesized by the transesterification method, the residual amount of carbonic acid diester is 300 ppm or less, preferably 200 ppm or less, and more preferably 150 ppm or less.

The molecular weight of the polycarbonate resin 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 in the range of 10,000 to 50,000, more preferably 10,000 to 40,000, and particularly preferably. Is in the range of 12,000 to 30,000. When the viscosity average molecular weight is 10,000 or more, the mechanical properties are exhibited more effectively, and when the viscosity average molecular weight is 50,000 or less, the molding process becomes easier. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed, or polycarbonate resins having a viscosity average molecular weight outside the above-mentioned preferable range may be mixed to be within the above-mentioned molecular weight range.

[Phosphorus flame retardant]
The phosphorus-based flame retardant used in the present invention is a phosphorus-based flame retardant containing phosphorus and liquid at room temperature. Here, "liquid at room temperature" means that it is liquid at 23 ° C.
Examples of the phosphorus-based flame retardant include phosphate-based compounds and condensed phosphoric acid esters, and condensed phosphoric acid ester is preferable.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、炭素数１～６のアルキル基またはアルキル基で置換されていてもよい炭素数６～２０のアリール基を示し、ｐ、ｑ、ｒおよびｓは、０または１であり、ｋは１から５の整数であり、Ｘ^１はアリーレン基を示す。） As the condensed phosphoric acid ester, a phosphoric acid ester compound represented by the following general formula (1), which is liquid at room temperature, is particularly preferable.

(In the formula, R ¹ , R ² , R ³ and R ⁴ represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and p, q, r and s are 0 or 1, k is an integer from 1 to 5, and X ¹ represents an arylene group.)

The phosphoric acid ester compound represented by the general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of phosphoric acid esters having different k, k is a mixture thereof. It becomes an average value. In the case of a mixture of compounds having different k-numbers, the average k-number is preferably 1-2, more preferably 1-1.5, even more preferably 1-1.2, particularly preferably 1-1.15. It is a range.

Further, X ¹ represents a divalent arylene group, for example, resorsinol, hydroquinone, bisphenol A, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene. It is the basis. Of these, divalent groups derived from bisphenol A, 3,3'-dihydroxybiphenyl are particularly preferred.

Further, p, q, r and s in the general formula (1) represent 0 or 1, respectively, and are preferably 1 among them.
Further, R ¹ , R ² , R ³ and R ⁴ each indicate an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such an aryl group include a phenyl group, a cresyl group, a xylyl group, an isopropylphenyl group, a butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a p-cumylphenyl group and the like. A group, a cresyl group and a xylyl group are more preferable.

Among the condensed phosphoric acid esters represented by the general formula (1), bisphenol A bis-diphenyl phosphate and the like are preferably mentioned as specific examples which are liquid at room temperature. Examples of commercially available products include "CR-741" manufactured by Daihachi Chemical Industry Co., Ltd. and "FP-600" manufactured by ADEKA Corporation.

[Stabilizer]
As the stabilizer used in the present invention, a phosphorus-based stabilizer or a phenol-based stabilizer is preferable.

Any known phosphorus-based stabilizer can be used. Specific examples are oxo acids of phosphorus such as phosphoric acid, phosphonic acid, phosphite, phosphinic acid and polyphosphate; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, potassium pyrophosphate, acidic calcium pyrophosphate; phosphoric acid. Phosphates of Group 1 or Group 2B metals such as potassium, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc., but organic phosphite compounds Especially preferable.

Examples of the organic phosphite compound include triphenylphosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl-phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and monooctyl. Diphenylphosphite, dioctylmonophenylphosphite, monodecyldiphenylphosphite, didecylmonophenylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, 2,2-methylenebis (4,6-di- tert-Butylphenyl) octylphosphite and the like can be mentioned.
Specific examples of such an organic phosphite compound include "ADEKA TAB 1178", "ADEKA STAB 2112", "ADEKA STAB HP-10" manufactured by ADEKA, and "JP-351" and "JP-351" manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include "JP-360", "JP-3CP", and "Irgafos 168" manufactured by BASF Corporation.
The phosphorus-based stabilizer may contain one kind or two or more kinds in any combination and ratio.

Examples of the phenol-based stabilizer include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 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-hydroxyphenyl) propionamide], 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 "-(mecitylene-2,4,6-triyl) tri-p- Cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene bis [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-triazine-2-ylamino ) Phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and the like.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are among them. preferable. Specific examples of such phenolic antioxidants include, for example, "Irganox 1010" and "Irganox 1076" manufactured by BASF, "ADEKA STAB AO-50" and "ADEKA STAB AO-60" manufactured by ADEKA. Can be mentioned.
In addition, 1 type may be contained in the phenol-based stabilizer, and 2 or more types may be contained in arbitrary combinations and ratios.

[High concentration phosphorus flame retardant masterbatch]
The high-concentration phosphorus-based flame retardant masterbatch of the present invention contains 55 to 75% by mass of a polycarbonate resin, 25 to 45% by mass of a phosphorus-based flame retardant liquid at room temperature, and 0 to 0.1% by mass of a stabilizer. .. Here, the ratio of each of the above components is the total mass% of these components based on 100% by mass.
The content of the phosphorus-based flame retardant liquid at room temperature in the masterbatch shall be 25% by mass or more and 45% by mass or less. The concentration of the liquid phosphorus flame retardant may be lower or higher than 25 to 45% by mass, and if it is out of the above range, the phosphorus flame retardant is localized in the polycarbonate resin and the flame retardant effect is exhibited. Deteriorate.
The masterbatch also preferably contains a stabilizer, and the content thereof is preferably 0 to 0.1% by mass. If the content of the stabilizer exceeds 0.1% by mass, the hue deteriorates, which is not preferable.

The preferred content of the high-concentration phosphorus-based flame retardant masterbatch of the present invention is 60 to 70% by mass of the polycarbonate resin, 30 to 40% by mass of the phosphorus-based flame retardant liquid at room temperature, and 0 to 0.08% by mass of the stabilizer. be.

[Manufacturing method of high-concentration phosphorus flame retardant masterbatch]
In the method for producing a high-concentration phosphorus-based flame retardant masterbatch of the present invention, a polycarbonate resin is supplied to a twin-screw extruder, the polycarbonate resin is melted in a kneading portion, and then a liquid phosphorus-based flame retardant at room temperature is applied to the whole. It is characterized in that it is supplied in an amount of 25 to 45% by mass, and the polycarbonate resin and the liquid phosphorus flame retardant are melt-kneaded in the kneading portion downstream of the extruder.

A twin-screw extruder is used in the method for producing the high-concentration phosphorus-based flame retardant masterbatch of the present invention. Various types of twin-screw extruders can be used, and the screw rotation method may be the same-direction rotation type or the reverse-direction rotation type, but the same-direction meshing type twin-screw extruder is preferable. The screw length, diameter, meshing ratio, etc. of the twin-screw extruder can be arbitrary or can be set arbitrarily. Further, the twin-screw extruder may be provided with a vent port that is depressurized or open to the atmosphere.

The polycarbonate resin is supplied from the supply port at the base of the twin-screw extruder, and the polycarbonate resin is melted at the first kneading portion. After the polycarbonate resin is melted, a phosphorus-based flame retardant that is liquid at room temperature is supplied from a supply port using a liquid supply pump or the like. The amount of the liquid phosphorus flame retardant supplied shall be 25 to 45% by mass with respect to the entire masterbatch. Then, the polycarbonate resin and the liquid phosphorus flame retardant are melt-kneaded in the second kneading section located downstream to produce a high-concentration phosphorus flame retardant masterbatch.

The screw configuration of the first kneading section and the second kneading section is a configuration in which a progressive kneading disc (R) is combined with an orthogonal kneading disc (N), a reverse feeding disc (L), and the like. Is preferable.
By supplying a liquid phosphorus-based flame retardant between the first kneading portion and the second kneading portion, the concentration of the liquid phosphorus-based flame retardant can be increased, and the screw having the above-mentioned preferable screw configuration can be increased. By shearing by rotation, the liquid phosphorus flame retardant is uniformly dispersed in the polycarbonate resin, and when used in the production of the polycarbonate resin composition, a high degree of flame retardancy can be stably exhibited.

The kneaded product melt-kneaded by the above method is extruded into a strand shape, then processed into pellets or flakes, each component is melt-kneaded using an extruder, and the kneaded product is extruded into a strand shape. After that, the kneaded product extruded into a strand shape is processed into a pellet shape, a flake shape, or the like, and is used as a high-concentration phosphorus-based flame retardant masterbatch for producing a flame-retardant polycarbonate resin composition.

[Flame-retardant polycarbonate resin composition]
The flame retardant polycarbonate resin composition of the present invention contains 62 to 75% by mass of the polycarbonate resin, 0.1 to 1% by mass of the fluororesin, 0.01 to 0.2% by mass of the stabilizer, and the above-mentioned high content. Concentration Phosphorus flame retardant masterbatch containing 25-38% by mass, or polycarbonate resin 52-73% by mass, fluorine-containing resin 0.1-1% by mass, core-shell type elastomer 2-10% by mass, stable It is characterized by containing 0.01 to 0.2% by mass of the agent and 25 to 38% by mass of the above-mentioned high-concentration phosphorus-based flame retardant masterbatch.
The content (mass%) of each of the above components means mass% based on a total of 100% by mass of each component.

The flame-retardant polycarbonate resin composition of the present invention is a resin composition containing the polycarbonate resin and the above-mentioned high-concentration phosphorus-based flame retardant masterbatch, as compared with the case where each component is kneaded without using the masterbatch. Therefore, it is possible to stably develop a high degree of flame retardancy, and it is possible to prevent bleed-out of the phosphorus-based flame retardant.
In addition, a liquid phosphorus-based flame retardant is master-batched at a high concentration to form a solid (pellet), which is then collectively fed to other essential raw materials, additional components to be blended for each grade, and an extruder. Since the desired flame-retardant polycarbonate resin composition can be produced by compounding once, it is extremely advantageous in terms of cost.

The flame-retardant polycarbonate resin composition of the present invention uses a polycarbonate resin, the above-mentioned high-concentration phosphorus-based flame retardant masterbatch, a fluororesin, a stabilizer, a core-shell elastomer if necessary, and other components used as necessary. Therefore, any conventionally known method can be appropriately selected for production.
Specifically, polycarbonate resin, the above-mentioned high-concentration phosphorus flame retardant masterbatch, fluororesin, stabilizer, core-shell elastomer if necessary, and other components used as needed, such as tumblers and henshell mixers. After mixing in advance using a mixer, the resin composition can be produced by melt-kneading with a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like.

The polycarbonate resin and stabilizer used in the flame-retardant polycarbonate resin composition are as described in the masterbatch section, and the same ones can be used.

[Fluororesin]
As the fluoroolefin resin, a fluoroolefin resin is preferable. The fluoroolefin resin is usually a polymer or a copolymer containing a fluoroethylene structure, and specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin is preferable.
Further, as the fluororesin, a resin having a fibril-forming ability is preferable, and specific examples thereof include a fluoroolefin resin having a fibril-forming ability. Having the ability to form fibrils tends to significantly improve the dripping prevention property during combustion.

Further, as the fluororesin, an organic polymer-coated fluoroolefin resin can also be preferably used. By using the organopolymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and foreign substances on the surface 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 coagulated or spray-dried to produce powder. A method of embodying and producing, (2) a method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then coagulating or spray-drying to powder. 3) A monomer having an ethylenically unsaturated bond is emulsion-polymerized in a dispersion of a mixture of an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, and then powdered by coagulation or spray drying. Examples thereof include a method of polymerizing and manufacturing.

As the monomer for producing the organic polymer that coats the fluoroolefin resin, one having a high affinity with the polycarbonate resin is preferable from the viewpoint of dispersibility when blended with the polycarbonate resin, and it is an aromatic vinyl type. More preferred are monomers, (meth) acrylic acid ester-based monomers, and vinyl cyanide-based monomers.

One type of fluororesin may be used, or two or more types may be used in any combination and in any ratio.

The content of the fluororesin in the flame-retardant polycarbonate resin composition is 0.1 to 1% by mass, preferably 0.1 to 0.5% by mass, based on 100% by mass of the total of the above components. ..

[Core-shell type elastomer]
As the core-shell type elastomer, a graft copolymer obtained by graft-polymerizing a rubber component with a monomer component copolymerizable therewith is preferable.

The method for producing such a graft copolymer may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, and the copolymerization method may be a one-step graft or a multi-step graft. May be good. Of these, emulsion polymerization is the easiest and preferred method.

The rubber component usually has a glass transition temperature of 0 ° C. or lower, particularly preferably −20 ° C. or lower, and more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, butadiene-acrylic composite rubber, styrene-butadiene rubber, ethylene-propylene-butadiene rubber and the like. These may be used alone or in admixture of two or more.

Specific examples of the rubber component and the monomer component that can be graft-copolymerized include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and glycidyl (meth) acrylate. Epoxy group-containing (meth) acrylic acid ester compounds, maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide, α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides. Examples include substances (eg, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable, and (meth) acrylic acid ester is more preferable, from the viewpoint of mechanical properties and surface appearance. It is a compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate. be able to.

The core-shell type elastomer used in the present invention is preferably a butadiene-based elastomer from the viewpoint of weld strength. Among them, a core-shell type graft copolymer having a polybutadiene-containing rubber component as a core layer and a shell layer formed by copolymerizing a methacrylic acid ester around the core layer is particularly preferable. The core-shell type graft copolymer preferably contains 40% by mass or more of a butadiene rubber component, and more preferably 60% by mass or more. Further, the methacrylic acid component is preferably contained in an amount of 10% by mass or more.

Preferred specific examples of such a core-shell type elastomer include a methyl methacrylate-butadiene-styrene graft copolymer, a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer, a methyl methacrylate-butadiene graft copolymer, and a methyl methacrylate-acrylic. -A butadiene rubber graft copolymer, a methyl methacrylate-acrylic butadiene rubber-styrene graft copolymer and the like can be mentioned. Such a rubbery polymer may be used alone or in combination of two or more.

The content of the core-shell type elastomer in the flame-retardant polycarbonate resin composition is 2 to 10% by mass, preferably 3 to 9% by mass, based on 100% by mass of the total of the above components.

[Other ingredients]
The flame-retardant polycarbonate resin composition of the present invention may contain other components in addition to those described above, if necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resin, various resin additives, and the like. In addition, 1 type may be contained in other components, and 2 or more types may be contained in arbitrary combinations and ratios.

<Other resins>
Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and the like. Astyrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resin such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; Polysulfonic resin; Polymethacrylate resin and the like can be mentioned.
In addition, 1 type may be contained in the other resin, and 2 or more types may be contained in arbitrary combinations and ratios.

When a resin other than the polycarbonate resin is contained, the content thereof is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and further 50 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Hereinafter, it is particularly preferable that the content is 40 parts by mass or less.

<Resin additive>
Examples of the resin additive include dyes and mold release agents, lubricants, fillers, ultraviolet absorbers, antistatic agents, antifog agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. Can be mentioned. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.

[Polycarbonate resin molded product]
The method for producing a molded product from the polycarbonate flame-retardant resin composition of the present invention is not particularly limited, and is a molding method generally adopted for a polycarbonate resin, that is, a general injection molding method or ultra-high-speed injection molding. Method, injection compression molding method, multicolor injection molding method, gas assisted injection molding method, molding method using heat insulating mold, molding method using rapid heating and cooling mold, foam molding (including supercritical fluid), insert Molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method and the like can be adopted. Further, in various injection molding methods, a molding method using a hot runner method can be selected.

The obtained molded products can be suitably used as electrical equipment, electronic equipment, vehicles such as automobiles, OA / information equipment such as printers and copiers, housing, construction, and other parts, and in particular, computers, personal computers, and various portables. It can be suitably used as a housing for a terminal, a battery, or the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not construed as being limited to the following examples.

Production Example 1
Polycarbonate resin "S3000F" (manufactured by Mitsubishi Engineering Plastics, trade name, viscosity average molecular weight 22000) is supplied to a twin-screw extruder (manufactured by Japan Steel Works, TEX44αII) at 120 kg / hr, and is supplied to the first kneading section (RRNNL). : The most upstream R is 1.0D in length, the other RNNL is 0.5D, D (screw diameter) = 44mm), and it is melt-kneaded. (Made by ADEKA, trade name, bisphenol A bis-diphenyl phosphate) is supplied at 80 kg / hr, kneaded with a polycarbonate resin in the second kneading section (RNL: each length is 0.5D) downstream of the supply, and from a die nozzle. It was extruded, cooled in a water tank, and pelletized to obtain a masterbatch pellet having a phosphorus flame retardant concentration of 40% by mass. The screw rotation speed was 700 rpm.
Here, R is a forward-feeding kneading disc having five paddles, N is an orthogonal kneading disc having five paddles, and L is a reverse-feeding kneading disc having five paddles. note that,

Manufacturing example 2
The concentration of the phosphorus-based flame retardant is 35 in the same manner as in Example 1 except that the supply amount of the polycarbonate resin "S3000F" is 130 kg / hr and the supply amount of the phosphorus-based flame retardant "FP-600" is 70 kg / hr. % Masterbatch pellets were obtained.

Production example 3
The concentration of the phosphorus-based flame retardant is 30 in the same manner as in Example 1 except that the supply amount of the polycarbonate resin "S3000F" is 140 kg / hr and the supply amount of the phosphorus-based flame retardant "FP-600" is 60 kg / hr. % Masterbatch pellets were obtained.

Production example 4
Further, the supply amount of the polycarbonate resin "S3000F" is 120 kg / hr, and the phosphorus-based stabilizer "ADEKA STUB 2112" (trade name, Tris (2,4-di-tert-butylphenyl) phosphite manufactured by ADEKA) is 0. The concentration of the phosphorus-based flame retardant was 40% and the concentration of the phosphorus-based stabilizer was 40% in the same manner as in Example 1 except that the supply amount of the phosphorus-based flame retardant "FP-600" was 80 kg / hr. A masterbatch pellet of 0.04% by mass was obtained.

Comparative manufacturing example 1
The concentration of the phosphorus-based flame retardant is 20 in the same manner as in Example 1 except that the supply amount of the polycarbonate resin "S3000F" is 160 kg / hr and the supply amount of the phosphorus-based flame retardant "FP-600" is 40 kg / hr. % Masterbatch pellets were obtained.

Comparative manufacturing example 2
The concentration of the phosphorus-based flame retardant is 50 in the same manner as in Example 1 except that the supply amount of the polycarbonate resin "S3000F" is 100 kg / hr and the supply amount of the phosphorus-based flame retardant "FP-600" is 100 kg / hr. % Masterbatch pellets were obtained.

The following polycarbonate resin composition was produced using the masterbatch obtained above.

Example 1
74.72 parts by mass of polycarbonate resin "S3000F", 0.2 parts by mass of tetrafluoroethylene resin "FA-500H" (manufactured by Daikin Industries, Ltd., trade name), phosphorus-based stabilizer "AS2112" (manufactured by ADEKA). Product name, Tris (2,4-di-tert-butylphenyl) phosphite, 0.03 parts by mass, phenol-based stabilizer "AO-60" (manufactured by ADEKA, product name, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) in 0.05 parts by mass, and the concentration of the phosphorus-based flame retardant obtained in Production Example 1 is 40% by mass in the masterbatch pellet 25. 00 parts by mass are mixed and supplied to the root hopper of the twin-screw extruder TEX44αII (screw configuration is the same as in Production Example 1) at 200 kg / hr, melt-kneaded at a screw rotation speed of 300 rpm, extruded from a die nozzle, and cooled in a water tank. Strand cutting was performed to obtain pellets of the polycarbonate resin composition.

Example 2
The same as in Example 1 except that the polycarbonate resin "S3000F" was made up to 71.15 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 35% by mass obtained in Production Example 2 was made up to 28.57 parts by mass. I went there.

Example 3
The same as in Example 1 except that the polycarbonate resin "S3000F" was 66.39 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 30% by mass obtained in Production Example 3 was 33.33 parts by mass. gone.

Example 4
74.72 parts by mass of polycarbonate resin "S3000F", 0.2 parts by mass of tetrafluoroethylene resin "FA-500H", 0.02 parts by mass of phosphorus-based stabilizer "AS2112", phenol-based stabilizer "AO-" 60 "by 0.05 parts by mass, and 25.01 parts by mass of the masterbatch pellet having a concentration of the phosphorus-based flame retardant obtained in Production Example 4 of 40% by mass and a concentration of the phosphorus-based stabilizer of 0.04% by mass. The mixture was mixed and supplied to the root hopper of the twin-screw extruder TEX44αII (screw configuration is the same as in Production Example 1) at 200 kg / hr, melt-kneaded at a screw rotation speed of 300 rpm, extruded from a die nozzle, cooled in a water tank, and strand-cut. Pellets of polycarbonate resin composition were obtained.

Comparative Example 1
Same as Example 1 except that the polycarbonate resin "S3000F" was 59.72 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 20% by mass obtained in Comparative Production Example 1 was 40.00 parts by mass. I went there.

Comparative Example 2
Same as Example 1 except that the polycarbonate resin "S3000F" was 79.72 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 50% by mass obtained in Comparative Production Example 2 was 20.00 parts by mass. I went there.

Comparative Example 3
Polycarbonate resin "S3000F" by 89.72 parts by mass, tetrafluoroethylene resin "FA-500H" by 0.2 parts by mass, phosphorus-based stabilizer "AS2112" by 0.03 parts by mass, phenol-based stabilizer "AO-" 60 ”0.05 parts by mass is mixed and supplied to the root of the screw configuration A so as to be 180 kg / hr in the same manner as in Example 1, and 10.00 parts by mass of the phosphorus flame retardant“ FP-600 ”is extruded. A liquid was added at 20 kg / hr between the root hopper and the first kneading portion, and the same procedure as in Example 1 was carried out below.

Example 5
Polycarbonate resin "S3000F" by 69.62 parts by mass, tetrafluoroethylene resin "FA-500H" by 0.3 parts by mass, core shell type elastomer "Kaneace M711" (manufactured by Kaneka Co., Ltd., trade name, methacrylate, butadiene, styrene) Polymer) by 5.0 parts by mass, the phosphorus-based stabilizer "AS2112" by 0.03 parts by mass, the phenol-based stabilizer "AO-60" by 0.05 parts by mass, and the phosphorus-based obtained in Production Example 1. 25.00 parts by mass of masterbatch pellets having a flame retardant concentration of 40% by mass are mixed and supplied to the root hopper of a twin-screw extruder TEX44αII (screw configuration is the same as in Production Example 1) at 200 kg / hr, and the screw rotation speed is increased. The mixture was melt-kneaded at 300 rpm, extruded from a die nozzle, cooled in a water tank, and strand-cut to obtain pellets of a polycarbonate resin composition.

Example 6
The same as in Example 5 except that the polycarbonate resin "S3000F" was 66.05 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 35% by mass obtained in Production Example 2 was 28.57 parts by mass. I went there.

Example 7
The same as in Example 5 except that the polycarbonate resin "S3000F" was 61.29 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 30% by mass obtained in Production Example 3 was 33.33 parts by mass. I went there.

Example 8
69.62 parts by mass of polycarbonate resin "S3000F", 0.3 parts by mass of tetrafluoroethylene resin "FA-500H", 5.0 parts by mass of core-shell type elastomer "Kaneace M711", phosphorus-based stabilizer "AS2112" 0.02 parts by mass, the phenol-based stabilizer "AO-60" by 0.05 parts by mass, the concentration of the phosphorus-based flame retardant obtained in Production Example 4 is 40% by mass, and the concentration of the phosphorus-based stabilizer is 0. 25.01 parts by mass of masterbatch pellets of .04 mass% was mixed and supplied to the root hopper of the twin-screw extruder TEX44αII (screw configuration is the same as in Production Example 1) at 200 kg / hr, and melt-kneaded at a screw rotation speed of 300 rpm. Then, it was extruded from a die nozzle, cooled in a water tank, and strand-cut to obtain pellets of a polycarbonate resin composition.

Comparative Example 4
Same as Example 5 except that the polycarbonate resin "S3000F" was 54.62 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 20% by mass obtained in Comparative Production Example 1 was 40.00 parts by mass. I went there.

Comparative Example 5
Same as Example 5 except that the polycarbonate resin "S3000F" was 74.62 parts by mass and the masterbatch pellet having a phosphorus-based flame retardant concentration of 50% by mass obtained in Comparative Production Example 2 was 20.00 parts by mass. I went there.

Comparative Example 6
84.62 parts by mass of polycarbonate resin "S3000F", 0.3 parts by mass of tetrafluoroethylene resin "FA-500H", 5.0 parts by mass of core-shell elastomer "Kaneace M711", and phosphorus-based stabilizer "AS2112". 0.03 parts by mass and 0.05 parts by mass of the phenol-based stabilizer "AO-60" were mixed and supplied to the root hopper of the twin-screw extruder TEX44αII (screw configuration is the same as in Production Example 1) at 180 kg / hr. 10.00 parts by mass of phosphorus-based flame retardant "FP-600" is liquid-added between the extruder root hopper and the first kneading part at 20 kg / hr, melt-kneaded at a screw rotation speed of 300 rpm, extruded from a die nozzle, and cooled in a water tank. And strand cut to obtain pellets of the polycarbonate resin composition.

UL94 test After drying the pellet of the polycarbonate resin composition obtained above at 120 ° C for 4 hours, a resin temperature of 280 ° C and a mold temperature of 80 were used using an injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.). UL test test pieces having a thickness of 0.8 mm were obtained under the condition of ° C.
The obtained UL test piece was conditioned for 48 hours in a high temperature room at 23 ° C and 50% relative humidity, and UL94 test (plastic for equipment parts) specified by the US Underwriters Laboratories (UL). The test was carried out in accordance with the material combustion test).
For the total flame burning time, the total burning time after 5 samples, that is, 10 times of flame contact in the 20 mm vertical combustion test of UL standard 94 is displayed in seconds. The total flame burning time is preferably 50 seconds or less, more preferably 40 seconds or less.
The evaluation results are shown in Table 1 below.

According to the present invention, a polycarbonate resin composition containing a liquid phosphorus flame retardant and exhibiting a high degree of flame retardancy can be stably obtained with high productivity, and can be used for electric devices, electronic devices, vehicles such as automobiles, printers and the like. It can be widely used for OA / information equipment such as copiers, materials for manufacturing parts in housing, construction, and other industrial fields, and has extremely high industrial utility.

Claims (4)

Based on a total of 100% by mass of the following components (A) to (D), (A) polycarbonate resin is 62 to 75% by mass, (B) fluororesin is 0.1 to 1% by mass, phosphorus-based stabilizer and / Alternatively, it contains 0.01 to 0.2% by mass of (C) stabilizer, which is a phenolic stabilizer , and 25 to 38% by mass of (D) masterbatch.
(D) The masterbatch contains 55 to 70% by mass of the polycarbonate resin, 30 to 45% by mass of the condensed phosphoric acid ester flame retardant liquid at room temperature, and an organic phosphite compound-based stabilizer and / or a phenol-based stabilizer. 0 to 0.1% by mass [(D) The total of each component in the masterbatch is 100% by mass. ] A flame-retardant polycarbonate resin composition comprising. Based on the total of 100% by mass of the following components (A) to (E), (A) polycarbonate resin is 52 to 73% by mass, (B) fluororesin is 0.1 to 1% by mass, phosphorus-based stabilizer and / Alternatively, it contains 0.01 to 0.2% by mass of (C) stabilizer, which is a phenolic stabilizer , 25 to 38% by mass of (D) master batch, and 2 to 10% by mass of (E) core-shell type elastomer. ,
(D) The masterbatch contains 55 to 70% by mass of the polycarbonate resin, 30 to 45% by mass of the condensed phosphoric acid ester flame retardant liquid at room temperature, and an organic phosphite compound-based stabilizer and / or a phenol-based stabilizer. 0 to 0.1% by mass [(D) The total of each component in the masterbatch is 100% by mass. ] A flame-retardant polycarbonate resin composition comprising. The method for producing the polycarbonate resin composition according to claim 1.
In the (D) master batch, the polycarbonate resin is supplied to the twin-screw extruder, and after the polycarbonate resin is melted in the kneading portion, a liquid condensed phosphoric acid ester flame retardant at room temperature is applied to the entire (D) from 30 to 30. A method for producing a flame-retardant polycarbonate resin composition, which comprises supplying in an amount of 45% by mass and melt-kneading a polycarbonate resin and a condensed phosphoric acid ester flame retardant in a kneading portion downstream of the extruder. The method for producing the polycarbonate resin composition according to claim 2.
In the (D) master batch, the polycarbonate resin is supplied to the twin-screw extruder, and after the polycarbonate resin is melted in the kneading portion, a liquid condensed phosphoric acid ester flame retardant at room temperature is applied to the entire (D) from 30 to 30. A method for producing a flame-retardant polycarbonate resin composition, which comprises supplying in an amount of 45% by mass and melt-kneading a polycarbonate resin and a condensed phosphoric acid ester flame retardant in a kneading portion downstream of the extruder.