JP6839501B2 - Polycarbonate resin composition and molded article - Google Patents

Description

The present invention relates to a polycarbonate resin composition and a molded product.

Polycarbonate resin is used for various purposes because it is excellent in transparency, impact resistance, heat resistance, and the like. When a polycarbonate resin composition containing such a polycarbonate resin is used for applications that generate high heat, a chlorine-based compound, a bromine-based compound, a phosphorus-based compound, or the like may be used as a constituent component of the resin composition. (For example, see Patent Document 1 below).

Japanese Unexamined Patent Publication No. 2006-299181

By the way, the polycarbonate resin composition may be required to further improve the flame retardancy that suppresses the combustion rate after ignition.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin composition having excellent flame retardancy that suppresses a combustion rate after ignition, and a molded product containing the resin composition. ..

The polycarbonate resin composition according to the present invention contains a polycarbonate resin and a glass filler, the average major axis of the glass filler is 1000 μm or less, and the total amount of the organic metal salt of sulfonic acid and the organic metal salt of sulfonamide. However, it is 1% by mass or less based on the total amount of the polycarbonate resin and the glass filler.

The polycarbonate resin composition according to the present invention has excellent flame retardancy that suppresses the combustion rate after ignition, and can reduce the maximum heat generation rate during combustion.

By the way, the polycarbonate resin composition may be required to have excellent ignition resistance for suppressing the ignition speed (time until ignition) in addition to flame retardancy for suppressing the combustion speed. On the other hand, the polycarbonate resin composition according to the present invention has excellent ignition resistance and can extend the ignition time. The polycarbonate resin composition as described above can suppress ignition and can suppress combustion after ignition.

The average major axis of the glass filler is preferably 10 to 1000 μm.

The total amount of the organometallic salt of sulfonic acid and the organometallic salt of sulfonamide may be more than 0% by mass and not more than 1% by mass based on the total amount of the polycarbonate resin and the glass filler.

The molded product according to the present invention contains the polycarbonate resin composition according to the present invention.

According to the present invention, it is possible to provide a polycarbonate resin composition having excellent flame retardancy that suppresses a combustion rate after ignition, and a molded product containing the resin composition. According to the present invention, it is possible to provide a polycarbonate resin composition having excellent ignition resistance in addition to flame retardancy, and a molded product containing the resin composition.

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means. The materials illustrated below may be used alone or in combination of two or more.

<Polycarbonate resin composition>
The polycarbonate resin composition according to the present embodiment contains (A) a polycarbonate resin (hereinafter, sometimes referred to as “(A) component”) and a glass filler (hereinafter, sometimes referred to as “(B) component”). However, the average major axis of the glass filler is 1000 μm or less, and the total amount of the organic metal salt of sulfonic acid and the organic metal salt of sulfonamide is 1% by mass or less based on the total amount of the polycarbonate resin and the glass filler. is there. The polycarbonate resin composition according to the present embodiment is at least one organic metal salt selected from the group consisting of a polycarbonate resin, a glass filler, an organic metal salt of sulfonic acid, and an organic metal salt of sulfonamide (hereinafter, depending on the case). It may be an embodiment containing (referred to as “component (C)”) and may be an embodiment containing no component (C).

The polycarbonate resin composition according to the present embodiment has excellent flame retardancy and ignition resistance. The present inventor presumes that the factors for obtaining such an effect are as follows. That is, in the polycarbonate resin composition according to the present embodiment, the polycarbonate resin and the specific glass filler were used, and the total amount of the organic metal salts was not more than a predetermined value, so that the composition was heated to a high temperature. Even if flammable gas is generated due to the decomposition of the resin composition, the flammable gas is retained inside due to the expansion of the resin composition, so that the flammable gas is suppressed from leaking to the outside. Further, when the total amount of the organometallic salts is not more than a predetermined value after using the polycarbonate resin and the specific glass filler, the decomposition rate of the resin composition is suppressed and the combustible gas is generated. Easy to be suppressed. As a result, the polycarbonate resin composition according to the present embodiment has excellent flame retardancy and ignition resistance.

(Component (A): Polycarbonate resin)
The polycarbonate resin as the component (A) can be obtained by, for example, a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester (diphenyl carbonate or the like). Examples of the polymer to be used. When producing the component (A), a molecular weight modifier, a catalyst, or the like can be used, if necessary.

Examples of the dihydroxydiaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), and 2,2. -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane , 1,1-bis (4-hydroxy-3-3rd butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5) Bis (hydroxyaryl) alkanes such as −dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cyclohexane; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; 4,4' Dihydroxydiarylsulfides such as −dihydroxydiphenylsulfide; dihydroxydiarylsulfoxides such as 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfoxide; 4,4′-dihydroxydiphenylsulfone, 4 , 4'-Dihydroxy-3,3'-Dihydroxydiarylsulfone such as dimethyldiphenylsulfone and the like. The dihydroxydiaryl compound may be used alone or in combination of two or more.

The dihydroxydiaryl compound may be used in combination with piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like.

A dihydroxydiaryl compound and a phenol compound having a valence of 3 or more may be used in combination. Examples of the trivalent or higher valent phenol compound include fluoroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene, and 2,4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl). Hydroxyphenyl) heptene, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis [4,54- (4,4') -Dihydroxydiphenyl) cyclohexyl] Propane and the like can be mentioned.

The viscosity average molecular weight of the component (A) is preferably 10,000 or more, more preferably 15,000 or more, further preferably 17,000 or more, particularly preferably 18,000 or more, and extremely preferably 20,000 or more, from the viewpoint of easily obtaining excellent moldability. .. The viscosity average molecular weight of the component (A) is preferably 100,000 or less, more preferably 35,000 or less, further preferably 28,000 or less, and 25,000 or less from the viewpoint that an excellent appearance of the surface of the molded product (sheet or the like) can be easily obtained. Especially preferable. From these viewpoints, the viscosity average molecular weight of the component (A) is preferably 1000 to 10000, more preferably 1500 to 35000, further preferably 17000 to 28000, particularly preferably 18000 to 25000, and extremely preferably 2000 to 25000. The viscosity average molecular weight of the component (A) can be obtained by the following procedure. First, a 0.5% by mass polycarbonate resin solution is obtained using methylene chloride as a solvent. _{Next, the specific viscosity (η sp} ) is measured at a temperature of 20 ° C. using a Canon Fenceke type viscosity tube. Then, the ultimate viscosity [η] can be obtained by concentration conversion, and the viscosity average molecular weight M can be calculated from the following SCHNELL formula.
[Η] = 1.23 × 10 ^-4 M ^0.83

The content of the component (A) is preferably in the following range based on the total amount of the component (A) and the component (B). The content of the component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of easily obtaining excellent moldability. It is preferable, and 70% by mass or more is extremely preferable. The content of the component (A) is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 87% by mass or less, from the viewpoint that an excellent appearance of the surface of the molded product (sheet or the like) can be easily obtained. Preferably, 85% by mass or less is particularly preferable, and 80% by mass or less is extremely preferable. From these viewpoints, the content of the component (A) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, further preferably 55 to 87% by mass, particularly preferably 60 to 85% by mass, and 70. ~ 80% by mass is extremely preferable.

The content of the component (A) is preferably in the following range based on the total mass of the resin composition. The content of the component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of easily obtaining excellent moldability. It is preferable, and 65% by mass or more is extremely preferable. The content of the component (A) is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 87% by mass or less, from the viewpoint that an excellent appearance of the surface of the molded product (sheet or the like) can be easily obtained. Preferably, 85% by mass or less is particularly preferable, 80% by mass or less is extremely preferable, and 70% by mass or less is very preferable. From these viewpoints, the content of the component (A) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, further preferably 55 to 87% by mass, particularly preferably 60 to 85% by mass, 65. ~ 80% by mass is extremely preferable, and 65 to 70% by mass is very preferable.

((B) component: glass filler)
The polycarbonate resin composition according to the present embodiment is a glass filler (glass) having an average major axis (average value of the longest diameter) of 1000 μm or less as the component (B) from the viewpoint of obtaining excellent flame retardancy and ignition resistance. Filler containing). When the average major axis of the glass filler exceeds 1000 μm, the distance between the glass fillers tends to be wide, and the flammable gas easily escapes from the gap between the glass fillers. Ignition resistance cannot be obtained.

The average major axis of the glass filler is preferably 800 μm or less, more preferably 600 μm or less, still more preferably 500 μm or less, from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. The average major axis of the glass filler is preferably 10 μm or more, more preferably 20 μm or more, further preferably 30 μm or more, and particularly preferably 40 μm or more, from the viewpoint that sufficient strength of the molded product can be easily obtained. From these viewpoints, the average major axis of the glass filler is preferably 10 to 1000 μm, more preferably 20 to 800 μm, further preferably 30 to 600 μm, and particularly preferably 40 to 500 μm.

The polycarbonate resin composition according to the present embodiment preferably contains a glass filler having the following average minor diameter (average value of the shortest diameter). The average minor axis of the glass filler is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 5 μm or more, from the viewpoint that sufficient strength of the molded product can be easily obtained. The average minor axis of the glass filler is preferably 25 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, and particularly preferably 12 μm or less, from the viewpoint that an excellent appearance of the surface of the molded product (sheet or the like) can be easily obtained. 10 μm or less is extremely preferable. From these viewpoints, the average minor axis of the glass filler is preferably 0.1 to 25 μm, more preferably 1 to 20 μm, further preferably 5 to 15 μm, particularly preferably 5 to 12 μm, and extremely preferably 5 to 10 μm.

The polycarbonate resin composition according to the present embodiment preferably contains a glass filler having the following average aspect ratio (average major axis / average minor axis). The average aspect ratio of the glass filler is preferably 1 or more, and more preferably 2 or more, from the viewpoint that an excellent appearance of the surface of the molded product (sheet or the like) can be easily obtained. The average aspect ratio of the glass filler is preferably 100 or less, more preferably 75 or less, further preferably 50 or less, particularly preferably 40 or less, and particularly preferably 30 or less, from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. Is extremely preferable, 20 or less is very preferable, 10 or less is further preferable, less than 5 is further preferable, and 4 or less is particularly preferable. From these viewpoints, the average aspect ratio of the glass filler is preferably 1 to 100, more preferably 1 to 75, further preferably 1 to 50, particularly preferably 1 to 40, extremely preferably 1 to 30, and 1 to 20. Is very preferable, 1 to 10 is even more preferable, 1 or more and less than 5 is further preferable, 1 to 4 is particularly preferable, and 2 to 4 is extremely preferable. The average aspect ratio of the glass filler may be 4 or more, 10 or more, 20 or more, or 40 or more.

The "major diameter (longest diameter) of the glass filler" is the length corresponding to the distance when the distance between the two plates is the largest when the glass filler is sandwiched between two parallel plates. Point to. The "minor diameter (shortest diameter) of the glass filler" is the length corresponding to the distance when the distance between the two plates is the smallest when the glass filler is sandwiched between two parallel plates. Point to. In a photographed image in which glass fillers arranged on a support (glass plate, etc.) so as not to overlap each other are observed with an optical microscope at a magnification of 40 to 500, each of 1000 arbitrarily selected glass fillers has a major axis or a minor axis. Can be obtained and the added average value can be obtained as the average major axis or the average minor axis. As the diameter of the glass filler (major diameter, minor diameter, etc.), the catalog value of a commercially available product can be adopted.

Examples of the shape of the glass filler include fibrous shape, flake shape (scale shape), and the like. Examples of the glass filler include milled fiber (glass fiber milled fiber), glass flakes, and glass beads. The "milled fiber" is a fibrous crushed product obtained by crushing glass fiber, and is, for example, a substantially columnar shape such as a columnar shape or a prismatic shape column. The milled fiber has the above-mentioned fiber length (fiber length of 1000 μm or less) as a major axis, and has a fiber diameter as a minor axis. By using the milled fiber, excellent flame retardancy and ignition resistance can be easily obtained. "Glass flakes" are flaky glass powders. The glass flakes have the above particle size (particle size of 1000 μm or less) as a major axis. "Glass beads" are spherical glass powders. By using the glass beads, the anisotropy of the shrinkage rate can be easily improved, and the warp of the molded product can be easily improved.

The polycarbonate resin composition according to this embodiment preferably contains milled fibers having the following average fiber diameters. The average fiber diameter of the milled fiber is preferably 1 μm or more, more preferably 5 μm or more, from the viewpoint that sufficient strength of the molded product can be easily obtained. The average fiber diameter of the milled fiber is preferably 25 μm or less, more preferably 15 μm or less, from the viewpoint that an excellent appearance of the surface of the molded product (sheet or the like) can be easily obtained. From these viewpoints, the average fiber diameter of the milled fiber is preferably 1 to 25 μm, more preferably 5 to 15 μm.

The polycarbonate resin composition according to the present embodiment preferably contains glass flakes having the following average minor diameter (for example, thickness). The average minor axis of the glass flakes is preferably 0.1 μm or more, and more preferably 1 μm or more, from the viewpoint that sufficient strength of the molded product can be easily obtained. The average minor axis of the glass flakes is preferably 10 μm or less, more preferably 8 μm or less, from the viewpoint that an excellent appearance of the surface of the molded product (sheet or the like) can be easily obtained. From these viewpoints, the average minor axis of the glass flakes is preferably 0.1 to 10 μm, more preferably 1 to 8 μm.

The glass filler may be a filler surface-treated with a surface treatment agent such as an organic silane compound or a silicone compound in order to improve the adhesiveness with the resin component.

One type of glass filler may be used alone, or two or more types may be used in combination. Each of the milled fibers, glass flakes, glass beads and the like may be used alone or in combination of two or more. The polycarbonate resin composition according to the present embodiment may be obtained by mixing a plurality of types of glass fillers (milled fiber, glass flakes, etc.) having different average major axis, average minor axis, average aspect ratio, etc. before mixing.

The content of the component (B) is preferably in the following range based on the total amount of the component (A) and the component (B). The content of the component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 13% by mass or more, and even more preferably 15% by mass, from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. Mass% or more is particularly preferable, and 20% by mass or more is extremely preferable. The content of the component (B) is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, and 40% by mass or less from the viewpoint that an excellent appearance of the molded product can be easily obtained. Is particularly preferable, and 30% by mass or less is extremely preferable. From these viewpoints, the content of the component (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, further preferably 13 to 45% by mass, particularly preferably 15 to 40% by mass, and 20%. ~ 30% by mass is extremely preferable.

The content of the component (B) is preferably in the following range based on the total mass of the resin composition. The content of the component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 13% by mass or more, and even more preferably 15% by mass, from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. Mass% or more is particularly preferable, and 20% by mass or more is extremely preferable. The content of the component (B) is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, and 40% by mass or less from the viewpoint that an excellent appearance of the molded product can be easily obtained. Is particularly preferable, and 35% by mass or less is extremely preferable. From these viewpoints, the content of the component (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, further preferably 13 to 45% by mass, particularly preferably 15 to 40% by mass, and 20%. ~ 35% by mass is extremely preferable.

The content of the component (B) is preferably in the following range based on the total mass of the component (A). The content of the component (B) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and even more preferably 40% by mass, from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. Mass% or more is particularly preferable. The content of the component (B) is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less, from the viewpoint that an excellent appearance of the molded product can be easily obtained. Is particularly preferable. From these viewpoints, the content of the component (B) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, further preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass.

(Component (C): Organometallic salt)
In the polycarbonate resin composition according to the present embodiment, the total amount of the component (C), which is an organic metal salt of sulfonic acid and an organic metal salt of sulfonamide, is 1% by mass or less based on the total amount of the polycarbonate resin and the glass filler. Is. Thereby, the flame retardancy and the ignition resistance of the polycarbonate resin composition can be improved.

Metals of organic metal salts include alkali metals, alkaline earth metals, aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn). , Zirconium (Zr), Molybten (Mo) and the like. Examples of the alkali metal include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and the like. Examples of the alkaline earth metal include magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and the like. The component (C) promotes the formation of a carbide layer during combustion of the polycarbonate resin composition, and further enhances flame retardancy and ignition resistance, as well as mechanical properties (for example, impact resistance) and heat resistance of the polycarbonate resin. , At least one selected from the group consisting of alkali metal salts (organic alkali metal salts) and alkaline earth metal salts (organic alkaline earth metal salts) is preferable from the viewpoint of maintaining good properties such as electrical properties. , Alkali metal salts are more preferred, and at least one selected from the group consisting of sodium salts, potassium salts and cesium salts is even more preferred.

As the organic metal salt, a metal salt of an aliphatic sulfonic acid, a metal salt of an aromatic sulfonic acid, a metal salt of an aliphatic sulfonic acid, and an aroma can be easily obtained from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. At least one selected from the group consisting of metal salts of group sulfonamides can be used.

Examples of the metal salt of the aliphatic sulfonic acid include a metal salt of a fluorine-containing aliphatic sulfonic acid. Examples of the metal salt of the fluoroaliphatic sulfonic acid include a metal salt of the fluoroaliphatic sulfonic acid having at least one CF bond in the molecule, and having at least one CF bond in the molecule. Examples thereof include alkali metal salts of fluoroaliphatic sulfonic acids and alkaline earth metal salts. Examples of the fluorine-containing aliphatic sulfonic acid having at least one CF bond in the molecule include perfluorobutane sulfonic acid and trifluoromethane sulfonic acid. Examples of the alkali metal salt of the fluoroaliphatic sulfonic acid having at least one CF bond in the molecule include lithium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, and perfluorobutanesulfon. Examples include cesium acid. Examples of the alkaline earth metal salt of fluoroaliphatic sulfonic acid having at least one CF bond in the molecule include magnesium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, barium perfluorobutane sulfonate, and trifluoromethane. Examples thereof include magnesium sulfonate, calcium trifluoromethanesulfonate, and barium trifluoromethanesulfonate.

Examples of the metal salt of aromatic sulfonic acid include a metal salt of aromatic sulfonic acid having at least one aromatic group in the molecule, and an alkali of aromatic sulfonic acid having at least one aromatic group in the molecule. Examples thereof include metal salts and alkaline earth metal salts. Examples of the aromatic sulfonic acid having at least one aromatic group in the molecule include diphenylsulfon-3,3'-disulfonic acid, diphenylsulfon-3-sulfonic acid, benzenesulfonic acid, (poly) styrenesulfonic acid, and paratoluene. Examples thereof include sulfonic acid, (branched) dodecylbenzenesulfonic acid, trichlorobenzenesulfonic acid, styrenesulfonic acid and the like. Examples of the alkali metal salt of aromatic sulfonic acid having at least one aromatic group in the molecule include diphenylsulfon-3,3'-dipotassium disulfonate, potassium diphenylsulfon-3-sulfonate, sodium benzenesulfonate, and benzenesulfon. Potassium oxyate, cesium benzene sulfonate, sodium (poly) styrene sulfonate, potassium (poly) styrene sulfonate, cesium (poly) styrene sulfonate, sodium paratoluene sulfonate, potassium paratoluene sulfonate, cesium paratoluene sulfonate, Examples thereof include (branched) sodium dodecylbenzenesulfonate, (branched) potassium dodecylbenzenesulfonate, (branched) cesium dodecylbenzenesulfonate, sodium trichlorobenzenesulfonate, potassium trichlorobenzenesulfonate, cesium trichlorobenzenesulfonate and the like. Examples of the alkaline earth metal salt of aromatic sulfonic acid having at least one aromatic group in the molecule include magnesium paratoluenesulfonic acid, calcium paratoluenesulfonate, strontium paratoluenesulfonate, and barium paratoluenesulfonic acid (branched). ) Magnesium dodecylbenzenesulfonate, (branched) calcium dodecylbenzenesulfonate and the like can be mentioned.

Examples of the metal salt of the aliphatic sulfonamide include a metal salt of the fluorine-containing aliphatic sulfonamide. Examples of the metal salt of the fluoroaliphatic sulfonamide include a metal salt of a linear fluoroaliphatic sulfonamide, a metal salt of a cyclic fluoroaliphatic sulfonamide, and the like, and an alkali metal of the linear fluoroaliphatic sulfonamide. Examples thereof include salts and alkaline earth metal salts, cyclic fluorine-containing aliphatic sulfonamide alkali metal salts and alkaline earth metal salts.

Examples of the linear fluorine-containing aliphatic sulfonamide include bis (trifluoromethanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, trifluoromethane (pentafluoroethane) sulfonylimide, and trifluoromethane (nonafluorobutane) sulfonylimide. Be done. Examples of the metal salt of the linear fluorine-containing aliphatic sulfonyl group include bis (trifluoromethanesulfonyl) imidelithium, bis (trifluoromethanesulfonyl) imide sodium, bis (trifluoromethanesulfonyl) imide potassium, and bis (nonafluorobutanesulfonyl) imidelithium. , Bis (nonafluorobutane sulfonyl) imide sodium, bis (nonafluorobutane sulfonyl) imide potassium, trifluoromethane (pentafluoroethane) sulfonylimide lithium, trifluoromethane (pentafluoroethane) sulfonylimide sodium, trifluoromethane (pentafluoroethane) Examples thereof include sulfonylimide potassium, trifluoromethane (nonafluorobutane) sulfonylimide lithium, trifluoromethane (nonafluorobutane) sulfonylimide sodium, trifluoromethane (nonafluorobutane) sulfonylimide potassium and the like.

Examples of the cyclic fluoroaliphatic sulfonamide include cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide and the like. Examples of the metal salt of the cyclic fluoroaliphatic sulfonamide include cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidelithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, and cyclo-hexa. Fluoropropane-1,3-bis (sulfonyl) imide potassium and the like can be mentioned.

Examples of the metal salt of the aromatic sulfonamide include a metal salt of the aromatic sulfonamide having at least one aromatic group in the molecule, and an alkali of the aromatic sulfonamide having at least one aromatic group in the molecule. Examples thereof include metal salts and alkaline earth metal salts. Aromatic sulfonamides having at least one aromatic group in the molecule include saccharin, N- (p-tolylsulfonyl) -p-toluenesulfoimide, N- (N'-benzylaminocarbonyl) sulfanylimide, N- (Phenylcarboxyl) -sulfanylimide and the like can be mentioned. Examples of the metal salt of the aromatic sulfonamide having at least one aromatic group in the molecule include a lithium salt of saccharin, a sodium salt and a potassium salt; a lithium salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide. Sodium salt and potassium salt; lithium salt of N- (N'-benzylaminocarbonyl) sulfanylimide, sodium salt and potassium salt; lithium salt of N- (phenylcarboxyl) -sulfanylimide, sodium salt, potassium salt and the like. ..

Among these, from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance, the group consisting of a metal salt of an aliphatic sulfonic acid, a metal salt of an aromatic sulfonic acid, and a metal salt of an aliphatic sulfonic acid At least one selected is preferable, and at least one selected from the group consisting of an alkali metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkali metal salt of an aliphatic sulfonic acid is more preferable and contains. At least one selected from the group consisting of an alkali metal salt of a fluoroaliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkali metal salt of a linear fluoroaliphatic sulfonic acid is more preferable. Alkali metal salts are particularly preferred. Specifically, it is selected from the group consisting of potassium perfluorobutanesulfonate, sodium paratoluenesulfonate, and bis (trifluoromethanesulfonyl) imide sodium from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. At least one of these is preferred. The component (C) may be used alone or in combination of two or more.

The content of the component (C) is 1% by mass or less based on the total amount of the components (A) and (B) from the viewpoint of obtaining excellent flame retardancy and ignition resistance. The content of the component (C) is from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance, from the viewpoint of excellent thermal stability of the resin composition, and from the viewpoint of excellent appearance and mechanical strength of the molded product. , 0.8% by mass or less is preferable, 0.7% by mass or less is more preferable, 0.5% by mass or less is further preferable, and 0.3% by mass is based on the total amount of the components (A) and (B). % Or less is particularly preferable, 0.1% by mass or less is extremely preferable, 0.08% by mass or less is very preferable, and 0.05% by mass or less is even more preferable. The content of the component (C) may be 0% by mass or more, may exceed 0% by mass, or 0.01% by mass, based on the total amount of the components (A) and (B). It may be more than or equal to, 0.02% by mass or more, and may be 0.04% by mass or more. From these viewpoints, the content of the component (C) is 0 to 1% by mass based on the total amount of the components (A) and (B), and is more than 0% by mass and 1% by mass or less. It may be 0.01 to 0.8% by mass, 0.02 to 0.7% by mass, 0.04 to 0.5% by mass, or 0. It may be 04 to 0.3% by mass, 0.04 to 0.1% by mass, 0.04 to 0.08% by mass, or 0.04 to 0.05. It may be% by mass.

The content of the component (C) is from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance, from the viewpoint of excellent thermal stability of the resin composition, and from the viewpoint of excellent appearance and mechanical strength of the molded product. Based on the total mass of the resin composition, 1% by mass or less is preferable, 0.8% by mass or less is more preferable, 0.7% by mass or less is further preferable, 0.5% by mass or less is particularly preferable, and 0. 3% by mass or less is extremely preferable, 0.1% by mass or less is very preferable, 0.08% by mass or less is further preferable, 0.05% by mass or less is further preferable, and 0.04% by mass or less is particularly preferable. The content of the component (C) may be 0% by mass or more, may exceed 0% by mass, or may be 0.01% by mass or more, based on the total mass of the resin composition. , 0.02% by mass or more, and may be 0.03% by mass or more. From these viewpoints, the content of the component (C) may be 0 to 1% by mass, or more than 0% by mass and 1% by mass or less, based on the total mass of the resin composition. It may be 0.01 to 0.8% by mass, 0.02 to 0.7% by mass, 0.03 to 0.5% by mass, or 0.03 to 0. .3 mass%, 0.03 to 0.1 mass%, 0.03 to 0.08 mass%, 0.03 to 0.05 mass% It may be 0.03 to 0.04% by mass.

The content of the component (C) is preferably in the following range based on the total mass of the component (A). The content of the component (C) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and more preferably 0.05% by mass from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. The above is more preferable, and 0.055% by mass or more is particularly preferable. The content of the component (C) is preferably 0.2% by mass or less, more preferably 0.15% by mass or less, and 0.12% by mass from the viewpoint of easily obtaining excellent flame retardancy and ignition resistance. The following is more preferable, and 0.1% by mass or less is particularly preferable. From these viewpoints, the content of the component (C) is preferably 0.01 to 0.2% by mass, more preferably 0.03 to 0.15% by mass, and further preferably 0.05 to 0.12% by mass. Preferably, 0.055 to 0.1% by mass is particularly preferable.

(Other ingredients)
The polycarbonate resin composition according to the present embodiment may be a known resin other than the above components (polyethylene, polyimide, polystyrene, ABS resin, polyolefin (polyethylene, polypropylene, etc.), polyester, phenol resin, epoxy resin, etc.), if necessary. Can be contained.

The polycarbonate resin composition according to the present embodiment may contain known additives other than the above-mentioned components, if necessary. Such additives include antioxidants (phosphorus antioxidants, phenolic antioxidants, etc.), UV absorbers, mold release agents (glycerin fatty acid esters, etc.), lubricants (paraffin wax, n-butyl stearate, etc.). , Synthetic beeswax, natural beeswax, glycerin monoester, montanic acid wax, polyethylene wax, pentaerythritol tetrastearate, etc.), colorants (titanium oxide, dyes, pigments, etc.), fillers (calcium carbonate, clay, silica, carbon black, etc.) , Carbon fiber, talc, mica, various whiskers, etc.), fluidity improver, spreading agent (epoxidized soybean oil, liquid paraffin, etc.), flame retardant, etc.

(Manufacturing method of polycarbonate resin composition)
The polycarbonate resin composition according to the present embodiment can be obtained by mixing the constituent components. The method for mixing the components is not particularly limited. For example, a method of mixing with an arbitrary mixer (tumbler, ribbon blender, high-speed mixer, etc.) and then melt-kneading with a single-screw extruder, twin-screw extruder, kneader, etc. Can be mentioned.

Each component is not mixed in advance, or only a part of the components are mixed in advance, and then the components are supplied to the extruder using a side feeder, and then melt-kneaded to produce a polycarbonate resin composition. You can also do it. In particular, in order to suppress the crushing of the glass filler, it is preferable to supply the glass filler from the side feeder installed on the downstream side of the extruder separately from the resin component and mix the resin component and the glass filler.

<Molded product and its manufacturing method>
The molded product according to the present embodiment includes the polycarbonate resin composition according to the present embodiment. The molded product according to the present embodiment may be in the form of a film or in the form of a flat plate. Examples of the molded product according to the present embodiment include a sheet and the like. The cross section of the molded product (sheet or the like) may be semi-circular or square. The surface of the molded product (sheet or the like) may be embossed or the like. From the viewpoint of further enhancing flame retardancy and ignition resistance, the surface of the molded product (sheet or the like) may be surface-treated with an inorganic substance or the like, or another layer may be laminated. The width of the sheet is, for example, 100 to 2000 mm. The thickness of the sheet is, for example, 0.1 to 5 mm.

The method for producing a molded product according to the present embodiment includes a molding step of molding the polycarbonate resin composition according to the present embodiment to obtain a molded product (sheet or the like). The molding method of the polycarbonate resin composition is not particularly limited, and is known as an extrusion molding method (T die molding method, calendar molding method, deformed extrusion method, etc.), compression molding method, injection molding method, injection / compression molding method, etc. Can be used.

The polycarbonate resin composition and molded body according to the present embodiment can be used in a wide range of fields, for example, home appliance members, electrical / electronic device members, OA device members, information terminal device members, mechanical parts, vehicle parts, and the like. It can be used in building members, lighting equipment members (for example, lighting covers, indicator lights and fluorescent tubes), daylighting members (for example, daylighting dome, skylights, arcades and road side wall boards), various containers and the like.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

<Making pellets>
Ingredients having the contents shown in Tables 1 and 2 were prepared. Next, the compounding components were melt-kneaded at a cylinder temperature of 280 ° C. using a twin-screw extruder having a diameter of 37 mm (manufactured by Kobe Steel, Ltd., trade name: KTX-37) to obtain various pellets.

The details of the ingredients used are as follows.

[Polycarbonate resin]
A-1: Polycarbonate resin synthesized from bisphenol A and phosgene, manufactured by Sumika Stylon Polycarbonate, trade name: Caliber 200-13 (viscosity average molecular weight: 21000)

[Glass filler]
B-1: Milled fiber, manufactured by Nitto Boseki Co., Ltd., trade name: PFE301S (average fiber length: 40 μm, average fiber diameter: 10 μm)
B-2: Milled fiber, manufactured by Nitto Boseki Co., Ltd., trade name: SS15-404 (average fiber length: 500 μm, average fiber diameter: 12 μm)
B-3: Glass flakes, manufactured by Nippon Sheet Glass Co., Ltd., trade name: REFG-313 (average particle size (major diameter): 150 μm, average thickness: 5 μm)
B-4: Chopped strand, manufactured by Owens Corning, trade name: FT737 (average fiber length: 3 mm, average fiber diameter: 13 μm)

[Organometallic salt]
C-1: Sodium paratoluenesulfonate, manufactured by Ton Fong Chemical; Industry Co, Ltd. C-2: Bis (trifluoromethanesulfonyl) imide sodium, manufactured by Mitsubishi Materials Electronics Chemicals Co., Ltd. C-3 : Potassium perfluorobutanesulfonate, manufactured by Rankses Co., Ltd.

<Manufacturing of flat plate>
The pellet was dried at 120 ° C. for 4 hours using a dryer. Next, using a compression molding machine (manufactured by Shinto Metal Industry Co., Ltd., trade name: NF.37), the molding temperature is 250 ° C., the mold temperature is 30 ° C., and the size is 100 mm × 100 mm × thickness 1.5 mm. A flat plate was obtained. Five flat plates were prepared for each of the examples and comparative examples.

<Evaluation: Combustion test>
^{Ignition time (unit: seconds) and maximum heat generation rate (unit: kW / m 2} ) were measured using a cone calorie meter (trade name: CONCALORIMETER III) manufactured by Toyo Seiki Co., Ltd. in accordance with ISO 5660-1. .. For each of the Examples and Comparative Examples, the five flat plates were measured and the average value was calculated. The flat plate was irradiated with heat rays for 10 minutes under the conditions of a heater set temperature of 750 ° C., a distance of 25 mm between the heater and the flat plate, and a radiation amount of 50.0 kW / m ^2. In addition, the presence or absence of expansion of the sample during combustion was visually observed. A case where sufficient expansion was observed was evaluated as "A", a case where slight expansion was observed was evaluated as "B", and a case where no expansion was observed was evaluated as "C". The results are shown in Tables 1 and 2.

As shown in Table 1, in the examples, expansion was observed during combustion, the ignition time was long, the maximum heat generation rate was small, and good results were obtained.

On the other hand, in Comparative Example 1 in which the glass filler was not used, expansion was not observed during combustion, and the maximum heat generation rate was significantly inferior.
In Comparative Examples 2 and 3 using a glass filler having a major axis exceeding 1000 μm, no expansion was observed during combustion, and both the ignition time and the maximum heat generation rate were inferior.
In Comparative Example 4 in which the content of the organometallic salt exceeded 1% by mass, although some expansion was observed during combustion, both the ignition time and the maximum heat generation rate were inferior.

Claims (3)

Containing polycarbonate resin and glass filler,
The average major axis of the glass filler is 1000 μm or less, and the glass filler has an average major axis of 1000 μm or less.
The average aspect ratio of the glass filler is 10 or less.
A polycarbonate resin composition in which the total amount of the organic metal salt of sulfonic acid and the organic metal salt of sulfonamide is more than 0% by mass and 1% by mass or less based on the total amount of the polycarbonate resin and the glass filler. The polycarbonate resin composition according to claim 1, wherein the glass filler has an average major axis of 10 to 1000 μm. A molded product containing the polycarbonate resin composition according to claim 1 or 2.