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, has advanced flame retardancy considering the environment, and also has excellent mechanical properties. The flame-retardant polycarbonate resin composition is characterized by containing 0.1 to 1.0 parts by mass of halloysite (B) and 0.01 to 5 parts by mass of a non-phosphorus or non-halogen-based flame retardant (C) with respect to 100 parts by mass of polycarbonate (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 an environmentally considerate material, has a high degree of flame retardancy, and also has excellent mechanical properties.

Background Art

[0002] Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical properties, and is widely used as a material for manufacturing parts in, for example, 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 parts 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 trend towards flame retardancy has increased, and high levels of flame retardancy have been required for polycarbonate resins. In many cases, V-0 products according to the UL-94 test method are required. As means for 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, and it is easy to reduce the mechanical properties of polycarbonate resin materials. Flame retardancy using halogen-based bromine-based or chlorine-based flame retardants has been subject to strengthened regulations on prohibited 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 a high degree of flame retardancy with a relatively small amount of blending. In addition, by blending such a flame retardant together 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, led by Japan, Europe, and the United States. PFAS regulations on perfluoroalkyl compounds and polyfluoroalkyl compounds have been advancing mainly in the EU and the United States, and polytetrafluoroethylene and the like are also targeted. PFAS regulations are being further strengthened internationally.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

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 as described above, 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 or a non-phosphorus-based flame retardant, or even without using polytetrafluoroethylene, which is 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 responds 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 halloysite and a non-phosphorus-based or non-halogen-based flame retardant, 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 1.0 parts by mass of halloysite (B) and 0.01 to 5 parts by mass of a non-phosphorus or non-halogen flame retardant (C) with respect to 100 parts by mass of polycarbonate (A). 2. The resin composition according to 1 above, wherein the non-phosphorus or non-halogen flame retardant (C) is a metal salt of an organic sulfonic acid. 3. The resin composition according to any one of 1 to 2 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). 4. The resin composition according to 3 above, wherein the filler (D) is a glass-based filler. 5. The resin composition according to 4 above, wherein the glass-based filler is glass fiber. 6. The resin composition according to any one of 1 to 5 above, further containing 0.1 to 2 parts by mass of a release agent (E) with respect to 100 parts by mass of the polycarbonate resin (A). 7. The resin composition according to any one of 1 to 6 above, having UL-94 of V-0 at a thickness of 1.5 mm. 8. Pellets of the resin composition according to any one of 1 to 7 above. 9. Molded articles of the resin composition according to any one of 1 to 7 above. 10. Molded articles of the pellets according to 8 above.

Advantages of the Invention

[0009] The flame-retardant polycarbonate resin composition of the present invention combines halloysite and a non-phosphorus or non-halogen flame retardant in a small addition amount with the polycarbonate resin, so that there is no generation of toxic gases during combustion, it complies with regulations such as PFAS, has a high degree of flame retardancy considering the environment, and also has excellent mechanical strength.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail by showing embodiments, examples, and the like. In this specification, “~” is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value, unless otherwise specified.

[0011] The flame-retardant polycarbonate resin composition of the present invention is characterized by containing 0.1 to 1.0 part by mass of halloysite (B) and 0.01 to 5 parts by mass of a non-phosphorus or non-halogen flame retardant (C) with respect to 100 parts by mass of polycarbonate (A).

[0012] [Polycarbonate resin (A)] The polycarbonate resin (A) used in the present invention is not particularly limited, and various types 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), aromatic polycarbonate resins are preferable from the viewpoints of heat resistance, mechanical properties, electrical properties, etc.

[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), and 1,4-dihydroxybenzene; Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl;

[0014] Dihydroxynaphthalenes 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, and 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, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-Dihydroxydiphenyl sulfone, Dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; etc. are mentioned.

[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), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) are preferred. In addition, 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, etc. 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; halocarbonates such as bis(chloroformate) of dihydroxy compounds and mono(chloroformate) 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 compounds of dihydroxy compounds such as bis(carbonate) of dihydroxy compounds, mono(carbonate) 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 the interfacial polymerization method, the melt transesterification method, the ring-opening polymerization method of cyclic carbonate compounds, the solid-phase transesterification method of prepolymers, etc. Among these, those by the interfacial polymerization method and the melt transesterification method are preferred because they have a higher effect of improving the moisture and heat resistance, and the interfacial polymerization method is particularly preferred.

[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, the decrease in 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 using the Schnell viscosity formula, that is, η = 1.23×10 -4 Mv 0.83 calculated therefrom. 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. Further, the content of the polycarbonate oligomer 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 material but also polycarbonate resin recycled from used products (so-called material recycled polycarbonate resin), and it is also preferable to contain both virgin polycarbonate resin and recycled polycarbonate resin, or it may consist of recycled polycarbonate resin. When containing recycled polycarbonate resin, the proportion of recycled polycarbonate resin 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] [Halloysite (B)] Halloysite (B) is a kind of clay mineral classified as a phyllosilicate mineral, and its chemical formula is represented by Al2Si2O5(OH)4. Halloysite has the same composition as kaolinite, but the bond between unit layers is weak, and it has a layered structure with water molecules incorporated between the layers, and has a roll-shaped tube-like form compared to the plate-like form generally observed in kaolinite.

[0030] The mechanism by which halloysite exhibits flame retardancy is that when exposed to high heat such as a flame, interlayer water and structural water are released, and due to its cooling and dilution effects, and also because the aluminol surface (-Al-OH + ) inside halloysite becomes an acid site, suppressing the formation of low molecular weight components by the cleavage reaction of the polycarbonate resin and facilitating the formation of a cross-linked structure by the isomerization reaction, and it is considered to be due to promoting good char formation.

[0031] Halloysite (B) is preferably surface-treated. Specific examples of the surface treatment agent include coupling agents such as silane-based coupling agents, titanate-based coupling agents, and aluminum-based coupling agents; alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol; alkanolamines such as triethylamine; organopolysiloxane and other organosilicon compounds; 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, silane-based coupling agents are preferred, and among them, silane-based coupling agents having a (meth)acrylic group, vinyl group, epoxy group, thiol group, benzotriazole group, or ethylene carbonate structure are preferred. In particular, (meth)acrylic silane-based coupling agents and the like are preferred, and those surface-treated with an acrylic silane having a (meth)acrylic group, particularly a methacrylic group, in the functional group are preferred.

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

[0033] The content of halloysite (B) is 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). With such a small content, the flame retardancy is good. If it is less than the above lower limit, the flame retardancy is insufficient. If the content exceeding the upper limit is increased, the decomposition of the polycarbonate proceeds and it is difficult to achieve good flame retardancy. The content of halloysite (B) is preferably 0.11 parts by mass or more, and preferably 0.9 parts by mass or less, particularly 0.8 parts by mass or less, 0.7 parts by mass or less, 0.6 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, 0.2 parts by mass or less, with respect to 100 parts by mass of the polycarbonate resin (A). The average particle diameter of halloysite (B) is the median particle diameter D50 of the particle size distribution obtained by measurement by the laser scattering method (ISO13320:2009), preferably 0.05 μm or more, more preferably 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, 6 μm or less, 4 μm or less, 2 μm or less.

[0034] [Phosphorus-free or halogen-free flame retardant (C)] The polycarbonate resin composition of the present invention contains a phosphorus-free and / or halogen-free flame retardant (C) that does not have a phosphorus atom or a halogen atom in its structural formula. Examples of the phosphorus-free and / or halogen-free flame retardant (C) include silicone flame retardants composed of silicone compounds, nitrogen-based flame retardants such as guanidine-based and melamine-based flame retardants, inorganic metal compounds, and other silicate minerals excluding halloysite (B). Among them, an organic sulfonic acid-based flame retardant having no fluorine atom is particularly preferred.

[0035] As the organic sulfonic acid-based flame retardant having no fluorine atom, a non-fluorine-based organic sulfonic acid or a metal salt thereof that does not have a C-F bond in the molecule is preferred. The metal of the metal salt is preferably an alkali metal or an alkaline earth metal, and examples thereof include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); and alkaline earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Among them, sodium, potassium, and cesium are preferred, and sodium and potassium are particularly preferred.

[0036] As the organic sulfonic acid or its metal salt having no fluorine atom, aromatic sulfonic acid or its metal salt, aromatic sulfonamide (or sulfonimide) or its metal salt, and polystyrene sulfonic acid or its metal salt are preferably mentioned, and more preferably these metal salts.

[0037] Examples of these specific examples 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 alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule include magnesium p-toluenesulfonate, calcium p-toluenesulfonate, strontium p-toluenesulfonate, barium p-toluenesulfonate, magnesium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, etc.

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

[0039] Among the above, as the organic sulfonic acid-based flame retardant having no fluorine atom, p-toluenesulfonic acid or its metal salt, phenylsulfonylbenzenesulfonic acid or its metal salt, polystyrenesulfonic acid or its metal salt are preferable, and among these, their metal salts, especially alkali metal salts, particularly sodium salt or potassium salt are preferable. The organic sulfonic acid-based flame retardant having no fluorine atom may be used alone, or two or more kinds may be used in combination at any combination and ratio.

[0040] The content of the non-phosphorus-based and / or non-halogen-based flame retardant (C) is 0.01 to 5 parts by mass, preferably 0.03 parts by mass or more, particularly preferably 0.05 parts by mass or more, 0.08 parts by mass or more, 0.10 parts by mass or more, based on 100 parts by mass of the polycarbonate resin (A). Also, it is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less, 1 part by mass or less. When the non-phosphorus-based and / or non-halogen-based flame retardant (C) is an organic sulfonic acid-based flame retardant having no fluorine atom, the content is 0.01 to 5 parts by mass, more preferably 0.02 parts by mass or more, particularly preferably 0.03 parts by mass or more, 0.05 parts by mass or more, 0.06 parts by mass or more, 0.07 parts by mass or more, 0.08 parts by mass or more, 0.09 parts by mass or more, 0.10 parts by mass or more, based on 100 parts by mass of the polycarbonate resin (A). Also, it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, particularly preferably 1 part by mass or less, 0.70 parts by mass or less, 0.50 parts by mass or less, 0.40 parts by mass or less, 0.30 parts by mass or less, 0.20 parts by mass or less. Further, the mass ratio (C / B) of the non-phosphorus-based and / or non-halogen-based flame retardant (C) to the haloite (B) is 0.3 or more and less than 1.5, preferably 0.5 or more, 0.6 or more, and preferably 1.45 or less, particularly preferably 1.4 or less, 1.35 or less, 1.25 or less. By doing so, a polycarbonate resin composition that clears PFAS regulations and achieves V-0 flame retardancy with a low addition amount can be obtained.

[0041] The polycarbonate resin composition of the present invention substantially does not contain a phosphorus-based flame retardant and / or a halogen-based flame retardant. Here, substantially not 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). With respect to 100 parts by mass of the polycarbonate resin (A), the filler (D) is preferably contained in an amount of 1 to 90 parts by mass, and by containing it together with the halloysite (B) and the non-phosphorus-based or non-halogen-based flame retardant (C), the flame retardancy by the halloysite (B) and the non-phosphorus-based or non-halogen-based flame retardant (C) and the sag prevention ability by the filler (D) function in a well-balanced manner, making it 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 with respect to 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, 60 parts by mass or less, 50 parts by mass or less. The filler (D) may contain only one kind or may contain two or more kinds.

[0043] As the filler (D), an inorganic filler is preferable, and the inorganic filler may be any of a needle-like inorganic filler, a fibrous inorganic filler, and a plate-like inorganic filler. The needle-like inorganic filler is an inorganic filler having a whisker-like, columnar, or the like 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. Further, as the shape of the fibrous inorganic filler, those in the form of chopped strands and milled fibers can be mentioned. The plate-like inorganic filler is an inorganic filler having a flaky, scaly, or the like shape, and examples thereof include talc, mica, and glass flakes.

[0044] The filler (D) is preferably a glass-based filler, and preferably exemplified by glass fiber, glass flake, glass bead, and glass balloon, and glass fiber and glass flake are particularly preferable. The composition of the raw material glass is preferably non-alkali, 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-section of the glass fiber. The glass fiber preferably has a number average fiber length (cut length) of 0.5 to 10 mm, 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, still more preferably 5.0 μm or more, and the upper limit is preferably 25.0 μm or less, more preferably 20 μm or less. Glass fibers having a flat cross-section are also preferred, with a flatness ratio of 1.5 to 8 being more preferred, and a flatness ratio of 2 to 6 being even more preferred. Examples of the glass flakes include scaly ones with a thickness of 0.5 to 20 μm and a side length of 0.05 to 1.0 mm.

[0046] The glass-based 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-based 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] The resin composition of the present invention preferably contains a release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 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 more preferred are aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms. 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 the aliphatic carboxylic acid and the alcohol, for example, the same ones as the above-mentioned aliphatic carboxylic acids 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] In addition, the above ester may contain an aliphatic carboxylic acid and / or an alcohol as impurities. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Furthermore, as the aliphatic carboxylic acid and the alcohol constituting one ester by bonding, each may be used alone or two or more thereof may be used in combination at an arbitrary combination and ratio.

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

[0053] Examples of aliphatic hydrocarbons 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 hydrocarbons include 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. Note that the aliphatic hydrocarbon may be a single substance, or a mixture of various components and molecular weights, and can be used as long as the main component is within the above range.

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

[0055] Note that the above-mentioned release agents may contain one kind, or may contain two or more kinds in any combination and ratio.

[0056] The content of the release agent is preferably 0.1 to 2 parts by mass, more preferably 1 part by mass or less, and even more 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 mold release property tends 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 as the stabilizer, a phosphorus-based stabilizer or a phenol-based stabilizer is preferable.

[0058] As the phosphorus-based stabilizer, any known one can be used. Specific examples include oxo acids of phosphorus such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic metal 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 preferable.

[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, didecylmonophenyl 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, and the like. The phosphorus-based stabilizer may be contained in one kind, or may be contained in 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, and usually 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less, based on 100 parts by mass of the polycarbonate resin (A). 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 become uneconomical.

[0061] Examples of phenolic stabilizers 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 these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Specific examples of such phenolic 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. In addition, the phenolic stabilizer may be contained singly or in any combination and ratio of two or more kinds.

[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, compatibilizers, etc. These additives may be contained singly or in two or more kinds.

[0065] In addition, it may contain other resins other than the polycarbonate resin (A). Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; styrene 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, etc. When containing other resins other than the polycarbonate resin (A), the content is preferably 45 parts by mass or less, particularly 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 especially 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 high 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 notchless Charpy impact strength with a thickness of 4.0 mm is 45 kJ / m 2 or more, preferably 50 kJ / m 2 or more can be achieved. In addition, the polycarbonate resin composition of the present invention is excellent in heat resistance, and the heat distortion temperature under the condition of a load of 1.80 MPa with a thickness of 4.0 mm is preferably 135 °C or higher, more preferably 140 °C or higher, particularly 141 °C or higher, 143 °C or higher, 144 °C or higher, and particularly preferably 145 °C or higher.

[0067] The polycarbonate resin composition of the present invention is molded into a molded article. As a method for manufacturing a molded article, a molding method generally adopted for a 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 method 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. In addition, a molding method using a hot runner system can also 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 molded products include parts for electric and electronic devices, office automation (OA) equipment, information terminal devices, machine parts, household appliances, vehicle parts, building materials, various containers, leisure goods and sundries, lighting equipment, etc. Among them, they are suitable for use in parts such as electric and electronic devices, OA equipment, information terminal devices, household appliances, lighting equipment, etc. For example, they are suitable for use in members for secondary battery devices used indoors or outdoors, members such as battery packs, storage batteries for electric bicycles, etc., and members for housings used outdoors.

Examples

[0069] Hereinafter, the present invention will be described more specifically by showing examples. However, the present invention is not 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 5) <Manufacture of resin composition pellets> Among the above-mentioned components, except for the filler (D), they were blended at the ratios (parts by mass) shown in Table 2 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 ratio (parts by mass) shown in Table 2 below, they were kneaded 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] <Fabrication of test pieces 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 produce test pieces 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 (1.5mmt)> The UL test specimens obtained above were tested in accordance with the UL94 test (combustion test for plastic materials for parts of equipment) specified by Underwriters Laboratories (UL) in the United States. The combustion results were classified as V-0, V-1, V-2 in descending order of good flammability, and those outside the specifications were classified as NR (not rated).

[0074] <Preparation of ISO multi-purpose test specimens (4mm)> After drying the resin composition pellets obtained above at 120°C for 4 hours, injection molding was carried out using an injection molding machine (NEX80III type) manufactured by Nissei Plastic Industrial Co., Ltd. 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 produce ISO multi-purpose test specimens (4 mm thick).

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

[0076] <Measurement of unnotched Charpy impact strength> Using the ISO multi-purpose test specimens (4mmt) obtained by the above method, the unnotched Charpy impact strength (unit: kJ / m 2 ) was measured in accordance with ISO 179-1 and ISO 179-2. 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 multi-purpose test specimens (4 mmt) obtained by the above method, the flexural modulus (unit: GPa) was measured in accordance with ISO 178.

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

[0079]

Table 2

Industrial Applicability

[0080] 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 polycarbonate (A), 0.1 to 1.0 part by mass of halloysite (B), and 0.01 to 5 parts by mass of a non-phosphorus-based or non-halogen-based flame retardant (C).

2. 2. The resin composition according to claim 1, wherein the non-phosphorus or non-halogen flame retardant (C) is an organic sulfonic acid metal salt.

3. 3. The resin composition according to claim 1, 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).

4. 4. The resin composition according to claim 3, wherein the filler (D) is a glass-based filler.

5. 5. The resin composition according to claim 4, wherein the glass-based filler is glass fiber.

6. 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).

7. 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.

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

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

10. A molded article made from the pellets according to claim 8.

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