Flame-retardant polycarbonate resin composition

Abstract

A flame-retardant polycarbonate resin composition that does not generate toxic gases during combustion, complies with regulations such as PFAS, is an advanced environmentally considerate flame-retardant material, and is excellent in heat resistance and impact resistance. A flame-retardant polycarbonate resin composition characterized by containing 0.1 to 2.5 parts by mass of sepiolite (B) and 0.01 to 5 parts by mass of an organic sulfonic acid metal salt (C) with respect to 100 parts by mass of a polycarbonate resin (A).

Description

Technical Field

[0001] The present invention relates to a flame-retardant polycarbonate resin composition. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition that clears PFAS regulations, is environmentally considerate, has high flame retardancy, and excellent mechanical properties.

Background Art

[0002] Polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical properties, and is widely used as a material for manufacturing parts in various fields such as vehicle parts, electrical and electronic equipment parts, housing members, and other industrial fields. In particular, flame-retardant polycarbonate resin compositions are preferably used as parts for vehicle parts, electrical and electronic equipment such as personal computers, mobile phones, battery cases, and parts for OA and information equipment such as printers and copiers.

[0003] In recent years, the demand for flame retardancy has increased, and high flame retardancy has been required for polycarbonate resins. In many cases, V-0 products according to the UL-94 test method are required. As a means of imparting flame retardancy to polycarbonate resins, halogen-based flame retardants and phosphorus-based flame retardants have been used. However, in order to exhibit V-0 flame retardant performance with a phosphorus-based flame retardant, a relatively large addition rate is required, which easily reduces the mechanical properties of the polycarbonate resin material. Flame retardancy using halogen-based bromine-based or chlorine-based flame retardants has been subject to strengthened regulations on the prohibition of use due to toxicity and environmental problems caused by the generation of harmful gases.

[0004] In particular, fluorine-based flame retardants typified by perfluoroalkane metal salts proposed in Patent Documents 1 and 2 enable high flame retardancy with a relatively small amount of compounding. In addition, by blending such a flame retardant with polytetrafluoroethylene as a dripping inhibitor, dripping can be suppressed and the flame retardancy can be further improved. However, in recent years, fluorine compounds have become an international regulatory target, particularly in Japan, Europe, and the United States. PFAS regulations regarding perfluoroalkyl compounds and polyfluoroalkyl compounds have been advancing mainly in the EU and the US, and also cover polytetrafluoroethylene and the like. PFAS regulations are being further strengthened internationally.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, a highly functional flame-retardant polycarbonate resin composition that does not generate toxic gases during combustion, complies with various regulations such as PFAS regulations, and is environmentally considerate is strongly desired. However, it is by no means easy to achieve V-0 in the UL-94 test without using a non-halogen-based flame retardant, a non-phosphorus-based flame retardant, or even without using polytetrafluoroethylene as a dripping inhibitor in combination. The present invention has been made in view of the above situation, and its object (problem) is to provide a polycarbonate resin composition having a high degree of flame retardancy that can respond to regulations such as PFAS and is environmentally considerate.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above problems, the present inventor has found that the above problems can be solved by containing sepiolite and a metal organic sulfonate, and has completed the present invention. The present invention relates to the following flame-retardant polycarbonate resin composition and molded article.

[0008] 1. A flame-retardant polycarbonate resin composition, characterized by containing 0.1 to 2.5 parts by mass of sepiolite (B) and 0.01 to 5 parts by mass of an organic sulfonic acid metal salt (C) with respect to 100 parts by mass of a polycarbonate resin (A). 2. The resin composition according to 1 above, wherein the sepiolite (B) is sepiolite surface-treated with a silicone compound. 3. The resin composition according to 1 or 2 above, wherein the organic sulfonic acid metal salt (C) is an aromatic sulfonic acid metal salt. 4. The resin composition according to any one of 1 to 3 above, further containing 1 to 90 parts by mass of a filler (D) with respect to 100 parts by mass of the polycarbonate resin (A). 5. The resin composition according to 4 above, wherein the filler (D) is a glass-based filler. 6. The resin composition according to 5 above, wherein the glass-based filler is glass fiber. 7. The resin composition according to any one of 1 to 6 above, further containing 0.1 to 2 parts by mass of a mold release agent (E) with respect to 100 parts by mass of the polycarbonate resin (A). 8. The resin composition according to any one of 1 to 7 above, wherein the content of sepiolite (B) is 0.1 part by mass or more and less than 1.0 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). 9. The resin composition according to any one of 1 to 8 above, wherein the UL-94 of 1.5 mm thickness is V-0. 10. Pellets of the resin composition according to any one of 1 to 9 above. 11. Molded articles of the resin composition according to any one of 1 to 9 above. 12. Molded articles of the pellets according to 10 above.

Advantages of the Invention

[0009] The flame-retardant polycarbonate resin composition of the present invention is an advanced flame-retardant resin material that takes into account the environment and clears regulations such as PFAS, with no generation of toxic gases during combustion, by using a combination of a low addition amount of sepiolite and an organic sulfonic acid metal salt in the polycarbonate resin, and is also excellent in heat resistance and impact resistance.

Modes for Carrying Out the Invention

[0010] Hereinafter, embodiments, exemplifications, etc. of the present invention will be shown and described in detail. In this specification, unless otherwise specified, "~" is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value.

[0011] The flame-retardant polycarbonate resin composition of the present invention is characterized by containing 0.1 to 2.5 parts by mass of sepiolite (B) and 0.01 to 5 parts by mass of an organic sulfonic acid metal salt (C) with respect to 100 parts by mass of the polycarbonate resin (A).

[0012] [Polycarbonate resin (A)] The polycarbonate resin (A) used in the present invention is not particularly limited, and various ones can be used. Polycarbonate resins can be classified into aromatic polycarbonate resins in which the carbon directly bonded to the carbonate bond is aromatic carbon, and aliphatic polycarbonate resins in which the carbon is aliphatic carbon, and either can be used. Among them, as the polycarbonate resin (A), from the viewpoints of heat resistance, mechanical properties, electrical properties, etc., an aromatic polycarbonate resin is preferable.

[0013] Among the monomers that are raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

[0014] dihydronaphthalenes such as 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene;

[0015] Dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene;

[0016] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-Bis(4-hydroxyphenyl)ethane, 1,1-Bis(4-hydroxyphenyl)-1-phenylethane, 1,1-Bis(4-hydroxyphenyl)-1-naphthylethane, 1,1-Bis(4-hydroxyphenyl)butane, 2,2-Bis(4-hydroxyphenyl)butane, 2,2-Bis(4-hydroxyphenyl)pentane, 1,1-Bis(4-hydroxyphenyl)hexane, 2,2-Bis(4-hydroxyphenyl)hexane, 1,1-Bis(4-hydroxyphenyl)octane, 2,2-Bis(4-hydroxyphenyl)octane, 4,4-Bis(4-hydroxyphenyl)heptane, 2,2-Bis(4-hydroxyphenyl)nonane, 1,1-Bis(4-hydroxyphenyl)decane, 1,1-Bis(4-hydroxyphenyl)dodecane, and bis(hydroxyaryl)alkanes such as;

[0017] 1,1-Bis(4-hydroxyphenyl)cyclopentane, 1,1-Bis(4-hydroxyphenyl)cyclohexane, 1,1-Bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-Bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-Bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane, 1,1-Bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-4-phenylcyclohexane, and other bis(hydroxyaryl) cycloalkanes;

[0018] 9,9-Bis(4-hydroxyphenyl)fluorene, Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0019] 4,4'-Dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-Dihydroxydiphenyl sulfone, Dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; and the like.

[0020] Among these, bis(hydroxyaryl) alkanes are preferred, and among them, bis(4-hydroxyphenyl) alkanes are preferred. Particularly, from the viewpoints of impact resistance and heat resistance, 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) are preferred. In addition, as for the aromatic dihydroxy compound, one kind may be used, or two or more kinds may be used in combination at an arbitrary combination and ratio.

[0021] Among the monomers that are raw materials for polycarbonate resins, examples of carbonate precursors include carbonyl halides, carbonate esters, and the like. Note that one type of carbonate precursor may be used, or two or more types may be used in combination at any arbitrary combination and ratio.

[0022] Specific examples of carbonyl halides include, for example, phosgene; haloformates such as bis-chloroformate forms of dihydroxy compounds and mono-chloroformate forms of dihydroxy compounds.

[0023] Specific examples of carbonate esters include, for example, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; carbonate forms of dihydroxy compounds such as bis-carbonate forms of dihydroxy compounds, mono-carbonate forms of dihydroxy compounds, and cyclic carbonates.

[0024] The method for producing the polycarbonate resin (A) is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a ring-opening polymerization method of a cyclic carbonate compound, a solid-phase transesterification method of a prepolymer, and the like. Among these, those by the interfacial polymerization method and the melt transesterification method are preferable from the viewpoint of having a higher effect of improving the moisture and heat resistance, and the interfacial polymerization method is particularly preferable.

[0025] The molecular weight of the polycarbonate resin (A) is the viscosity average molecular weight (Mv) converted from the solution viscosity measured at a temperature of 25 °C using methylene chloride as a solvent, preferably 10,000 to 50,000, more preferably 11,000 to 40,000, particularly preferably 12,000 to 35,000, and especially preferably 13,000 to 30,000. By setting the viscosity average molecular weight to be not less than the lower limit value of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved. By setting the viscosity average molecular weight to be not more than the upper limit value of the above range, a decrease in the fluidity of the polycarbonate resin composition of the present invention can be suppressed and improved, and the molding processability can be enhanced to facilitate the molding process. In addition, two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed.

[0026] The viscosity average molecular weight [Mv] means a value obtained by using methylene chloride as a solvent, determining the intrinsic viscosity [η] (unit: dl / g) at a temperature of 25 °C using an Ubbelohde viscometer, and applying Schnell's viscosity formula, that is, η = 1.23×10 -4 Mv 0.83 It is calculated from. The intrinsic viscosity [η] is a value measured for the specific viscosity [η sp at each solution concentration [C] (g / dl) and calculated by the following formula.

Equation

[0027] In addition, in order to improve the appearance and fluidity of the molded product, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate oligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[0028] Furthermore, the polycarbonate resin (A) may be not only virgin raw materials but also polycarbonate resins recycled from used products (so-called material-recycled polycarbonate resins). It is also preferable to contain both virgin polycarbonate resins and recycled polycarbonate resins, and it may also consist of recycled polycarbonate resins. When containing recycled polycarbonate resins, the proportion of recycled polycarbonate resins in the polycarbonate resin (A) is preferably 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, and it is also preferable that the recycled polycarbonate resin is 100%.

[0029] [Sepiolite (B)] Sepiolite (B) is a type of clay mineral classified as a phyllosilicate mineral, and its chemical formula is Mg8Si 12 O 30 (OH)4(OH2)4·8H2O. Sepiolite is a fibrous mineral composed of discontinuous layers, is porous, has a large specific surface area, and has high adsorbability for water and the like.

[0030] The mechanism by which sepiolite exhibits flame retardancy is considered to be that when exposed to high heat such as a flame, interlayer water and structural water are released, resulting in a cooling and dilution effect, and that the fiber structure of sepiolite reinforces the formed char.

[0031] Sepiolite (B) is preferably surface-treated. Specific examples of the surface treatment agent include silicone compounds such as organopolysiloxane, silane coupling agents, titanate coupling agents, coupling agents such as aluminum coupling agents, alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, higher fatty acids such as stearic acid, fatty acid metal salts such as calcium stearate and magnesium stearate, polyacrylate salts such as sodium polyacrylate and ammonium polyacrylate, hydrocarbon lubricants such as polyethylene wax and liquid paraffin, basic amino acids such as lysine and arginine, polyglycerin and their derivatives, and the like. Among these, silicone compounds such as organopolysiloxane are preferable. Surface treatment with a silicone compound improves heat resistance, has good dispersibility in the polycarbonate resin, and has a large flame retardancy improvement effect, so it is preferable.

[0032] Sepiolite is commercially available, and commercially available sepiolite can also be used as sepiolite (B).

[0033] The content of sepiolite (B) is 0.1 to 2.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). With such a small content, good flame retardancy is achieved. If it is less than the above lower limit, the flame retardancy is insufficient, and if it is contained in an amount exceeding the upper limit, the decomposition of the polycarbonate proceeds and it is difficult to achieve good flame retardancy. The content of sepiolite (B) is preferably 0.11 parts by mass or more, more preferably 0.12 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). Also, it is more preferably 2.3 parts by mass or less, especially 2.0 parts by mass or less, 1.8 parts by mass or less, 1.5 parts by mass or less, 1.3 parts by mass or less, 1.1 parts by mass or less, 1.0 parts by mass or less, less than 1.0 parts by mass, 0.9 parts by mass or less, 0.8 parts by mass or less, and particularly preferably less than 0.8 parts by mass. By setting it below the above upper limit, the decomposition of the resin is suppressed, and the deflection temperature under load at a thickness of 4.0 mm tends to improve.

[0034] [Metal salt of organic sulfonic acid (C)] The polycarbonate resin composition of the present invention contains a metal salt of organic sulfonic acid (C). As the metal salt of organic sulfonic acid (C), a non-fluorine-based metal salt of organic sulfonic acid flame retardant having no C-F bond in the molecule is preferable.

[0035] The metal of the metal salt is preferably an alkali metal or an alkaline earth metal, and examples include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs); alkaline earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba). Among them, sodium, potassium, and cesium are preferable, and sodium and potassium are particularly preferable.

[0036] As the metal salt of organic sulfonic acid (C), metal salts of aromatic sulfonic acids, metal salts of aromatic sulfonamides (or sulfonimides), and metal salts of polystyrene sulfonic acids are preferably mentioned.

[0037] Specific examples thereof include, for example, potassium 3-(phenylsulfonyl)benzenesulfonate (i.e., potassium diphenylsulfone-3-sulfonate), dipotassium diphenylsulfone-3,3'-disulfonate, sodium benzenesulfonate, potassium benzenesulfonate, cesium benzenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, cesium p-toluenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, cesium dodecylbenzenesulfonate, potassium styrenesulfonate, sodium polystyrenesulfonate, potassium polystyrenesulfonate, cesium polystyrenesulfonate, etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule; Examples of the alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule include magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, and the like.

[0038] Examples of the metal salts of aromatic sulfonamides (or sulfonimides) include potassium salt of N-(p-toluenesulfonyl)-p-toluenesulfonimide, potassium salt of N-(N'-benzylaminocarbonyl)sulfanylimide, potassium salt of N-(phenylcarboxyl)-sulfanylimide, and the like.

[0039] Among the above-mentioned organic sulfonic acid metal salts (C), metal salts of paratoluenesulfonic acid, metal salts of phenylsulfonylbenzenesulfonic acid, and metal salts of polystyrenesulfonic acid are preferable, and among these, these metal salts, particularly alkali metal salts, especially sodium salt or potassium salt are preferable. The organic sulfonic acid metal salt (C) may be used alone or in combination of two or more in any combination and ratio.

[0040] The content of the organic sulfonic acid metal salt (C) is 0.01 to 5 parts by mass, preferably 0.02 parts by mass or more, among which 0.03 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, 0.1 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), and preferably 4 parts by mass or less, more preferably 3 parts by mass or less, among which 2 parts by mass or less, 1.5 parts by mass or less, 1.0 parts by mass or less, 0.7 parts by mass or less, 0.5 parts by mass or less, 0.4 parts by mass or less, 0.3 parts by mass or less, particularly preferably 0.2 parts by mass or less. The mass ratio (C / B) of the content of the organic sulfonic acid metal salt (C) to the sepiolite (B) is 0.06 to 1.9, preferably 0.075 or more, 0.1 or more, 0.2 or more, 0.3 or more, and preferably 1.75 or less, particularly preferably 1.5 or less, 1.25 or less, 1.1 or less. By doing so, it is possible to clear PFAS regulations and achieve a polycarbonate resin composition with V-0 flame retardancy at a low addition amount, and the mechanical properties and thermal properties are also improved.

[0041] In addition, the polycarbonate resin composition of the present invention preferably does not substantially contain a phosphorus-based flame retardant or a halogen-based flame retardant. Here, not substantially containing means that the amount of the phosphorus-based flame retardant and / or the halogen-based flame retardant is preferably less than 0.05 parts by mass, more preferably less than 0.03 parts by mass, particularly preferably less than 0.01 parts by mass, less than 0.005 parts by mass, less than 0.001 parts by mass, and particularly preferably less than 0.0005 parts by mass, respectively or in total, based on 100 parts by mass of the polycarbonate resin (A).

[0042] [Filler (D)] The polycarbonate resin composition of the present invention preferably further contains a filler (D). By containing the filler (D) in an amount of preferably 1 to 90 parts by mass based on 100 parts by mass of the polycarbonate resin (A) and together with the sepiolite (B) and the organic sulfonic acid metal salt (C), the flame retardancy ability of the sepiolite (B) and the organic sulfonic acid metal salt (C) and the sag prevention ability of the filler (D) can function in a well-balanced manner, and it becomes possible to achieve a higher degree of flame retardancy. The content of the filler (D) is more preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, 7 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more based on 100 parts by mass of the polycarbonate resin (A), and more preferably 80 parts by mass or less, particularly preferably 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less. The filler (D) may contain only one type or two or more types.

[0043] As the filler (D), an inorganic filler is preferable, and the inorganic filler may be any of a needle-shaped inorganic filler, a fibrous inorganic filler, and a plate-shaped inorganic filler. The needle-shaped inorganic filler is an inorganic filler having a shape such as a whisker shape or a column shape, and examples thereof include wollastonite. The fibrous inorganic filler refers to a thin and long fibrous inorganic filler, and examples thereof include glass fiber, ceramic fiber, and carbon fiber. In addition, examples of the fibrous inorganic filler in terms of shape include chopped strand and milled fiber. The plate-shaped inorganic filler is an inorganic filler having a shape such as a flake shape or a scaly shape, and examples thereof include talc, mica, and glass flake.

[0044] The filler (D) is preferably a glass-based filler, and preferably exemplified by glass fiber, glass flake, glass bead, and glass balloon, etc., and glass fiber and glass flake are more preferable. The composition of the raw material glass is preferably alkali-free, and examples thereof include E glass, C glass, S glass, R glass, etc., and E glass is preferably used.

[0045] In addition to the general circular shape, various irregular cross-sectional shapes may be used for the cross-sectional shape of the glass fiber. The glass fiber preferably has a number average fiber length (cut length) of 0.5 to 10 mm, and more preferably 1.0 to 5.0 mm. The number average fiber diameter of the glass fiber is preferably 4.0 μm or more, more preferably 4.5 μm or more, further preferably 5.0 μm or more, and the upper limit is preferably 25.0 μm or less, and more preferably 20 μm or less. Glass fiber having a flat cross-section is also preferable, and the flatness ratio is more preferably 1.5 to 8, and further preferably 2 to 6. Examples of the glass flake include scaly ones having a thickness of 0.5 to 20 μm and a side length of 0.05 to 1.0 mm.

[0046] The glass filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. The adhesion amount of the surface treatment agent is preferably 0.01 to 1% by mass of the glass filler. Further, if necessary, lubricants such as fatty acid amide compounds and silicone oils, antistatic agents such as quaternary ammonium salts, resins having film-forming ability such as epoxy resins and urethane resins, and those surface-treated with a mixture of a resin having film-forming ability and a heat stabilizer, a flame retardant, etc. can also be used.

[0047] [Release agent (E)] The resin composition of the present invention preferably contains a release agent (E). Examples of the release agent (E) include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbons having a number average molecular weight of 200 to 15000, polysiloxane-based silicone oils, and the like.

[0048] Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetratriacontanoic acid, montanic acid, adipic acid, azelaic acid, and the like.

[0049] As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, for example, the same as the above aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have substituents such as fluorine atoms and aryl groups. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferred. Here, aliphatic is used as a term including alicyclic compounds.

[0050] Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like.

[0051] Note that the above ester may contain an aliphatic carboxylic acid and / or an alcohol as impurities. Also, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, for the aliphatic carboxylic acid and the alcohol that combine to form one ester, each may use one kind, or two or more kinds may be used in combination in any combination and ratio.

[0052] Specific examples of the ester of an aliphatic carboxylic acid and an alcohol include beeswax (a mixture mainly composed of myricyl palmitate), stearyl stearate, behenyl behenate, behenyl stearate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, and the like.

[0053] Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include, for example, liquid paraffin, paraffin wax, micro wax, polyethylene wax, Fischer-Tropsch wax, α-olefin oligomers having 3 to 12 carbon atoms, and the like. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized. Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. Further, the number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less. The aliphatic hydrocarbon may be a single substance, or may be a mixture of various components and molecular weights, as long as the main component is within the above range, it can be used.

[0054] Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, fluorinated alkyl silicone, and the like.

[0055] In addition, the above-mentioned release agent may contain one kind, or may contain two or more kinds in any combination and ratio.

[0056] The content of the release agent (E) is preferably 0.1 to 2 parts by mass, more preferably 1 part by mass or less, still more preferably 0.8 part by mass or less, and particularly preferably 0.5 part by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). When the content of the release agent is less than the lower limit value of the above range, the effect of releasability is likely to be insufficient, and when it exceeds the upper limit value of the above range, there may be a decrease in hydrolysis resistance and mold contamination during injection molding.

[0057] [Stabilizer] The polycarbonate resin composition of the present invention preferably contains a stabilizer, and phosphorus-based stabilizers and phenol-based stabilizers are preferable as the stabilizer.

[0058] As the phosphorus stabilizer, any known one can be used. Specific examples include oxoacids of phosphorus such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 2 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Among them, organic phosphite compounds are particularly preferred.

[0059] Examples of the organic phosphite compound include triphenyl phosphite, tris(monononylphenyl) phosphite, tris(monononyl / dinonyl phenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecyldiphenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, etc. Examples of such organic phosphite compounds include "ADEKA STAB 1178", "ADEKA STAB 2112", "ADEKA STAB HP-10" manufactured by ADEKA Corporation, "JP-351", "JP-360", "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., "IRGAFOS 168" manufactured by BASF Corporation, etc. In addition, the phosphorus stabilizer may contain one kind, or may contain two or more kinds in any combination and ratio.

[0060] The content of the phosphorus-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, based on 100 parts by mass of the polycarbonate resin (A), and is usually 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less. When the content of the phosphorus-based stabilizer is less than the lower limit of the above range, the thermal stability effect may be insufficient. When the content of the phosphorus-based stabilizer exceeds the upper limit of the above range, the effect may reach a plateau and may not be economical.

[0061] Examples of the phenolic stabilizer include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[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]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-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-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0062] 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 preferable. Specific examples of such hindered phenol antioxidants include, for example, "Irganox 1010" and "Irganox 1076" manufactured by BASF, "Adekastab AO-50" and "Adekastab AO-60" manufactured by ADEKA, and the like. The phenolic stabilizer may be contained in one kind, or may be contained in two or more kinds in any combination and ratio.

[0063] The content of the phenolic stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass or less, based on 100 parts by mass of the polycarbonate resin (A). By setting the content of the phenolic stabilizer to be equal to or higher than the lower limit value of the above range, the effect as a phenolic stabilizer can be sufficiently obtained, and by setting it to be equal to or lower than the upper limit value of the above range, the effect does not reach a plateau and it is economical.

[0064] [Additives, etc.] The polycarbonate resin composition of the present invention can contain other additives other than those described above, for example, additives such as ultraviolet absorbers, fluorescent brighteners, pigments, dyes, plasticizers, and compatibilizers. These additives may be contained singly or in combination of two or more.

[0065] In addition, it is also possible to contain other resins in an amount less than that of the polycarbonate resin (A). Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; styrenic resins such as polystyrene resin, high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polymethacrylate resin, and the like. When containing other resins other than the polycarbonate resin (A), the content is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, and particularly preferably 1 part by mass or less, based on 100 parts by mass of the polycarbonate resin (A). In particular, when containing polybutylene terephthalate resin, the content is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, and particularly preferably 1 part by mass or less, based on 100 parts by mass of the polycarbonate resin (A).

[0066] [Polycarbonate Resin Composition] The polycarbonate resin composition of the present invention has a high degree of flame retardancy and can achieve V-0 with a UL test piece having a thickness of 1.5 mm in the UL-94 test. In addition, the polycarbonate resin composition of the present invention is excellent in impact resistance, and the Izod impact strength without notch having a thickness of 4.0 mm is preferably 50 kJ / m 2 or more, more preferably 55 kJ / m 2 or more, still more preferably 57 kJ / m 2 or more, particularly 59 kJ / m 2 or more is preferable. Moreover, the polycarbonate resin composition of the present invention is excellent in heat resistance, and has a heat distortion temperature under the condition of a load of 1.80 MPa and a thickness of 4.0 mm of 135°C or higher, preferably 140°C or higher, and particularly preferably 143°C or higher, 144°C or higher, especially 145°C or higher.

[0067] The polycarbonate resin composition of the present invention is molded into a molded article. As the manufacturing method of the molded article, a molding method generally adopted for the polycarbonate resin composition can be arbitrarily adopted. Examples thereof include injection molding method, ultra-high-speed injection molding method, injection compression molding method, two-color molding method, hollow molding methods such as gas assist, molding method using a heat-insulating mold, molding method using a rapid heating mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, lamination molding method, press molding method, blow molding method, etc. Also, a molding method using a hot runner system can be used. Among them, injection molding methods such as injection molding method, ultra-high-speed injection molding method, and injection compression molding method are preferable.

[0068] [Molded article] Examples of the molded article include parts of electric and electronic equipment, OA equipment, information terminal equipment, machine parts, household appliances, vehicle parts, building members, various containers, leisure goods and sundries, lighting equipment, etc. Among them, it is suitable for use in parts of electric and electronic equipment, OA equipment, information terminal equipment, household appliances, lighting equipment, etc. For example, it is suitable for use in members for secondary battery devices used indoors or outdoors, members such as battery packs, battery members for electric bicycles, etc., and members for housings used outdoors.

Examples

[0069] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not to be construed as being limited to the following examples. The components used in the examples and comparative examples are as shown in Table 1 below.

[0070]

Table 1

[0071] (Examples 1 to 10, Comparative Examples 1 to 6) <Manufacture of Resin Composition Pellets> Among the above-described components, except for the filler (D), they were blended at the ratios (parts by mass) shown in Tables 2 and 3 below, mixed in a tumbler for 20 minutes, and then supplied to a twin-screw extruder "TEX30α" manufactured by Japan Steel Works, Ltd. equipped with 1 vent. While further supplying the filler (D) from the middle of the barrel by a side feeder at the ratios (parts by mass) shown in Tables 2 and 3 below, kneading was carried out under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 25 kg / hr, and a barrel temperature of 280°C. The molten resin extruded in a strand shape was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of the polycarbonate resin composition.

[0072] <Preparation of Test Specimens for UL-94> After drying the resin composition pellets obtained by the above manufacturing method at 120°C for 4 hours, using a SE100DU type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., injection molding was carried out under the conditions of a cylinder temperature of 300°C, a mold temperature of 110°C, and a molding cycle of 40 seconds to injection mold test specimens for UL-94 with a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm.

[0073] <Flammability Evaluation: UL-94 (1.5 mm t)> The test specimens for UL test obtained above were tested in accordance with the UL94 test (combustion test for plastic materials for parts of equipment) defined by Underwriters Laboratories, Inc. (UL) in the United States. The combustion results were ranked from good as V-0, V-1, V-2, and those outside the standard were classified as NR (not rated).

[0074] <Preparation of ISO Multipurpose Test Specimens (4 mm)> After drying the resin composition pellets obtained above at 120°C for 4 hours, using an injection molding machine (NEX80III type) manufactured by Nissei Plastic Industrial Co., Ltd., injection molding was carried out under the conditions of a cylinder set temperature of 280°C, a mold temperature of 80°C, an injection time of 2 seconds, and a molding cycle of 50 seconds to injection mold ISO multipurpose test specimens (4 mm thick).

[0075] <Measurement of heat resistance (heat deflection temperature)> Using the ISO multipurpose test specimen (thickness 4 mm) obtained above, based on the ISO 75 A method, the heat deflection temperature (DTUL, unit: °C) was measured under the condition of a load of 1.80 MPa.

[0076] <Measurement of unnotched Charpy impact strength> Using the ISO multipurpose test specimen (4 mm t) obtained by the above method, in accordance with ISO 179-1 and ISO 179-2, the unnotched Charpy impact strength (unit: kJ / m 2 ) was measured. When the test specimen was not broken in this measurement, it was designated as NB (No Break).

[0077] <Measurement of flexural modulus> Using the ISO multipurpose test specimen (4 mm t) obtained by the above method, in accordance with ISO 178, the flexural modulus (unit: GPa) was measured.

[0078] The above results are shown in Tables 2 and 3 below. In the table, Example n is Example n and Comparative Example n is Comparative Example n.

[0079]

Table 2

[0080]

Table 3

Industrial Applicability

[0081] The polycarbonate resin composition of the present invention is a polycarbonate resin material that does not generate toxic gases during combustion, clears regulations such as PFAS, exhibits excellent flame retardancy at a low addition amount, and also has excellent mechanical properties, so it can be suitably used for various molded products.

Claims

1. A flame-retardant polycarbonate resin composition comprising 100 parts by mass of a polycarbonate resin (A), 0.1 to 2.5 parts by mass of sepiolite (B), and 0.01 to 5 parts by mass of an organic sulfonic acid metal salt (C).

2. 2. The resin composition according to claim 1, wherein the sepiolite (B) is a sepiolite surface-treated with a silicone compound.

3. 3. The resin composition according to claim 1, wherein the organic sulfonic acid metal salt (C) is an aromatic sulfonic acid metal salt.

4. The resin composition according to claim 1 or 2, further comprising a filler (D) in an amount of 1 to 90 parts by mass per 100 parts by mass of the polycarbonate resin (A).

5. 5. The resin composition according to claim 4, wherein the filler (D) is a glass-based filler.

6. 6. The resin composition according to claim 5, wherein the glass-based filler is glass fiber.

7. The resin composition according to claim 1 or 2, further comprising a release agent (E) in an amount of 0.1 to 2 parts by mass per 100 parts by mass of the polycarbonate resin (A).

8. The resin composition according to claim 1 or 2, wherein the content of the sepiolite (B) is 0.1 part by mass or more and less than 1.0 part by mass per 100 parts by mass of the polycarbonate resin (A).

9. The resin composition according to claim 1 or 2, wherein the UL-94 rating of the composition at a thickness of 1.5 mm is V-0.

10. A pellet of the resin composition according to claim 1 or 2.

11. A molded article made from the resin composition according to claim 1 or 2.

12. A molded article made from the pellets according to claim 10.

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