Insulation flame-retardant resin composition, and molded article and sheet

Abstract

To provide an insulation flame-retardant resin composition which is excellent in flame retardancy, tracking resistance, mold releasability and heat stability, and a molded article and a sheet.SOLUTION: An insulation flame-retardant resin composition contains, with respect to (A) 100 pts.wt. of a polycarbonate resin (component A), (B) 0.5 to 1.8 pts.wt. of a flame retardant (component B), where the flame retardant is a nitrogen-containing compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a flame-retardant insulating resin composition having excellent flame retardancy, tracking resistance, mold releasability and thermal stability, as well as a molded article and a sheet. [Background technology]

[0002] Polycarbonate resins have excellent mechanical properties and are widely used in automobile peripheral parts, battery peripheral parts, etc. In recent years, the development of batteries and electric vehicles has been active in order to reduce CO2 emissions, and there is a high demand for materials that are flame retardant and have excellent tracking resistance that can withstand high voltages from the perspective of safety. Conventionally, a method for improving flame retardancy has been used in which a flame retardant is blended to impart flame retardancy to resin molded products. For example, in order to improve the flame retardancy of polycarbonate resins, a method of blending a large amount of an oligomer or polymer of a carbonate derivative of brominated bisphenol A has been used. However, since a large amount of flame retardant is added, there are many problems, such as the generation of halogenated gases that are harmful to the human body during combustion. Therefore, there is a demand for a flame-retardant resin composition using a flame retardant that does not generate halogen-containing gases.

[0003] Patent Document 1 discloses a thermoplastic resin composition containing ammonium polyphosphate, a phosphorus-containing compound, and a nitrogen-containing cyclic compound as a flame retardant. However, although a large amount of ammonium polyphosphate and a nitrogen-containing cyclic compound are used in combination as a flame retardant, there is a problem that the flame retardancy is insufficient. Patent Documents 2 and 3 disclose a flame-retardant resin composition consisting of a polycarbonate resin, a low molecular weight phosphate ester compound as a flame retardant, and a fibrous material. However, when a low molecular weight phosphate ester compound such as an aromatic diphosphate is used as a flame retardant, a large amount of the compound must be added to impart flame retardancy, and the generation of char is also promoted, resulting in a problem that the electrical conductivity is increased and the tracking resistance is deteriorated. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2000-154322 A [Patent Document 2] JP 2002-30209 A [Patent Document 3] JP 2002-226694 A Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the above, an object of the present invention is to provide a flame-retardant insulating resin composition, and a molded article and sheet thereof, which are excellent in flame retardancy, tracking resistance, mold releasability and thermal stability. [Means for solving the problem]

[0006] According to the present invention, the above problems are solved by the following configuration. 1. An insulating flame-retardant resin composition comprising 100 parts by weight of (A) polycarbonate resin (component A) and 0.5 to 1.8 parts by weight of (B) flame retardant (component B), wherein the flame retardant is a nitrogen-containing compound. 2. The insulating flame-retardant resin composition according to the above item 1, wherein the nitrogen-containing compound is melamine cyanurate. 3. The insulating flame-retardant resin composition according to item 1 or 2 above, which comprises 0.05 to 1.8 parts by weight of (C) carbon black (component C) per 100 parts by weight of component A. 4. The insulating flame-retardant resin composition according to any one of items 1 to 3 above, wherein component A has a viscosity average molecular weight of 17,000 to 25,500. 5. The insulating flame-retardant resin composition according to any one of items 1 to 4 above, wherein component B is a nitrogen-containing compound in which the proportion of particles having a particle size of 50 μm or more as measured by a microtrack method is less than 0.1%. 6. A molded article or sheet obtained by molding the flame-retardant insulating resin composition according to any one of items 1 to 5 above. Effect of the Invention

[0007] The insulating and flame-retardant resin composition of the present invention is excellent in flame retardancy, tracking resistance, mold release property, and thermal stability, and thus is widely useful in electrical and electronic applications, automotive peripheral component applications, battery peripheral component applications, and other various applications. Among them, it provides a molded product that is extremely useful as an electrical and electronic application, an automotive peripheral component application, and a battery peripheral component application, and the industrial effect achieved by the present invention is extremely large.

Mode for Carrying Out the Invention

[0008] Hereinafter, the details of the present invention will be further described.

[0009] <Component A: Polycarbonate Resin> The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

[0010] Representative examples of the dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5-dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4- 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene Examples of the 4,4'-dihydroxydiphenyl ether include isopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl ester. These can be used alone or in combination of two or more.

[0011] Among them, homopolymers or copolymers obtained from at least one bisphenol selected from the group consisting of bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferred, and in particular, homopolymers of bisphenol A and copolymers of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane with bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, or α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferably used.

[0012] The carbonate precursor may be a carbonyl halide, a carbonate ester or a haloformate, and specific examples thereof include phosgene, diphenyl carbonate or a dihaloformate of a dihydric phenol.

[0013] When the dihydric phenol and the carbonate precursor are reacted by the interfacial polycondensation method or the melt transesterification method to produce the polycarbonate resin, a catalyst, a terminal terminator, an antioxidant for the dihydric phenol, etc. may be used as necessary. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, or a mixture of two or more of the obtained polycarbonate resins.

[0014] Reaction methods such as the interfacial polymerization method, melt transesterification method, solid-phase transesterification method of carbonate prepolymer, and ring-opening polymerization method of cyclic carbonate compound for the production method of the polycarbonate resin of the present invention are well-known methods in various literatures and patent gazettes and the like.

[0015] When the viscosity-average molecular weight of the polycarbonate resin is less than 17,000, cracks may occur during molding. When it exceeds 25,500, the fluidity deteriorates and the molding processability may decrease. Therefore, it is preferably 17,000 to 25,500, more preferably 17,000 to 25,400, and even more preferably 17,300 to 25,000.

[0016] Two or more polycarbonate resins may be mixed. In this case, it is of course possible to mix a polycarbonate resin whose viscosity-average molecular weight is outside the above range.

[0017] The viscosity-average molecular weight referred to in the present invention is the specific viscosity (η SP ) obtained from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C and is determined by inserting it into the following formula. η SP / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23×10 -4 M 0.83 c = 0.7

[0018] <Component B: Flame Retardant> The flame retardant used as component B of the present invention is a nitrogen-containing compound, preferably melamine cyanurate. Specific examples of melamine cyanurate include MC25 (manufactured by BASF, D50: 1.5 μm, D99: 11.6 μm), MC6000 (manufactured by Nissan Chemical Industries, D50: 1.8 μm, D99: 8.3 μm), MC4000 (manufactured by Nissan Chemical Industries, D50: 14.1 μm, D99: 58.8 μm), MC7000 (manufactured by Nissan Chemical Industries, D50: 1.9 μm, D99: 3.0 μm), MC-20S (manufactured by Sakai Chemical Industry, D50: 3.2 μm, D99: 10.1 μm), and MC-2010N (manufactured by Sakai Chemical Industry, D50: 3.1 μm, D99: 9.9 μm). Here, D50 and D99 were measured by the laser analysis / scattering method using SALD-3000S manufactured by SHIMADZU Corporation. D99 is preferably from 1 μm to 10 μm, more preferably from 3 μm to 9 μm, and even more preferably from 5 μm to 9 μm. When D99 is within this range, the balance of flame retardancy, tracking resistance, and sheet mass productivity may be more excellent. These compounds can be used alone or in combination with other flame retardants. When a flame retardant other than a nitrogen-containing compound is used as the flame retardant, it is difficult to achieve both flame retardancy and tracking resistance.

[0019] Component B is preferably a nitrogen-containing compound in which the proportion of particles having a particle size of 50 μm or more measured by the microtrack method is less than 0.1%, and more preferably less than 0.05%. When the proportion is less than 0.1%, the proportion of small particle size particles increases, and flame retardancy can be efficiently exhibited in a small amount. The lower limit of the proportion is preferably 0%.

[0020] The content of component B is 0.5 to 1.8 parts by weight, preferably 0.55 to 1.79 parts by weight, more preferably 0.6 to 1.78 parts by weight, and even more preferably 0.6 to 1.3 parts by weight with respect to 100 parts by weight of component A. When the content of component B is less than 0.5 part by weight, the flame retardancy deteriorates, and when it exceeds 1.8 parts by weight, the flame retardancy and thermal stability deteriorate.

[0021] <Component C: Carbon black> The method for adding carbon black used in the present invention is not particularly limited, but from the viewpoint of workability, it is preferable to use a masterbatch obtained by premixing and masterbatch blending with a polycarbonate resin. The kneading method is not particularly limited, but kneading by an extruder is preferable.

[0022] The content of component C is preferably 0.05 to 1.8 parts by weight, more preferably 0.06 to 1.79 parts by weight, still more preferably 0.07 to 1.78 parts by weight, particularly preferably 0.08 to 1.77 parts by weight, and most preferably 0.08 to 1.6 parts by weight, based on 100 parts by weight of component A. If the content of component C is less than 0.05 parts by weight, concealing properties may not be imparted by the molded product, and if it exceeds 1.8 parts by weight, the conductivity may increase and the tracking resistance may deteriorate.

[0023] <Regarding the manufacturing method of the insulating and flame-retardant resin composition> The insulating and flame-retardant resin composition of the present invention can be produced by any method. For example, it is produced by kneading with a single-screw or multi-screw extruder. It can be prepared by feeding component A, which is a polycarbonate resin, component B, which is a flame retardant, and optionally other components into an extruder by a feeder. The insulating and flame-retardant resin composition thus obtained can be made into a molded product or a sheet for use in automotive parts and battery peripheral parts, etc., by various known methods, such as injection molding and sheet molding.

Examples

[0024] Hereinafter, the insulating and flame-retardant resin composition of the present invention will be specifically described based on examples. "Parts" in the following measurement conditions and examples, etc. each represent "parts by weight".

[0025] <Materials used> <Component A: Polycarbonate resin> A-1: L-1250WQ (trade name) (manufactured by Teijin Limited, viscosity average molecular weight 25,100) A-2: L-1250WP (trade name) (manufactured by Teijin Limited, viscosity average molecular weight 23,800) A-3: L-1225WX (Product Name) (manufactured by Teijin Limited, viscosity average molecular weight 19,700) <Component B: Flame Retardant> B-1: MC25 (Product Name) (manufactured by BASF, melamine cyanurate, D50: 1.5 μm, D99: 11.6 μm, proportion of particles with a particle size of 50 μm or more measured by the Microtrac method is less than 0.1%) B-2 (Comparative Example): PX-200 (Product Name) (manufactured by Daihachi Chemical Industry Co., Ltd., condensed phosphate ester) B-3: MC6000 (Product Name) (manufactured by Nissan Chemical Industries, melamine cyanurate, D50: 1.8 μm, D99: 8.3 μm, proportion of particles with a particle size of 50 μm or more measured by the Microtrac method is less than 0.1%) B-4: MC7000 (Product Name) (manufactured by Nissan Chemical Industries, melamine cyanurate, D50: 1.9 μm, D99: 3.0 μm, proportion of particles with a particle size of 50 μm or more measured by the Microtrac method is less than 0.1%) <Component C: Carbon Black> C-1: 650B (Product Name) (manufactured by Mitsubishi Chemical Corporation, particle size 22 nm)

[0026] <Manufacture of Insulating Flame Retardant Resin Composition> (Examples 1 - 9, Comparative Examples 1 - 3) The components shown in Table 1 were premixed at the ratios shown in Table 1, and each was melt-kneaded using a twin-screw extruder [TEX30α-3, manufactured by Japan Steel Works, Ltd.] at 250 °C, and pellets were produced while degassing with a vacuum vent.

[0027] <Evaluation Method> The obtained pellets were dried in a hot air circulation dryer at 120 °C for 5 hours or more, and then each test piece was prepared and judged by the following evaluation method. The results are shown in Table 2.

[0028] 1. Flame Retardancy Using an injection molding machine [NEX50-5E, manufactured by Nissei Plastics], 0.3 mmt test pieces (125 mm x 13 mm x 0.3 mmt) were made under the following conditions: cylinder temperature 280°C, mold temperature 80°C, injection speed 270 mm / sec. After that, they were conditioned for 48 hours under conditions of 23°C x 50% humidity, and the flame retardancy was evaluated according to the UL94 test (flammability test for plastic materials for equipment parts), with V-0 being passed and other cases being failed. The UL94 classes are shown in Table 1.

[0029] [Table 1]

[0030] 2. Tracking resistance The tracking resistance was evaluated by the following method. It is necessary to pass tracking resistance I, and it is preferable to pass tracking resistance II. 1) Tracking resistance I Using an injection molding machine [ROBOSHOT α-S100iA, manufactured by FANUC], two 2mmt test pieces (50mm x 90mm x 2mmt) were molded at a cylinder temperature of 260°C and a mold temperature of 65°C. In this state, a voltage of 600V was applied using a tracking tester [YST-112, manufactured by Yamayo Tester] and a 0.1% aqueous solution of ammonium chloride was dropped every 30 seconds. If no tracking occurred for 100 drops, it was considered a pass, and if tracking occurred, it was considered a fail. 2) Tracking resistance II Using an injection molding machine [ROBOSHOT α-S100iA, manufactured by FANUC], a 3 mmt test piece (50 mm x 90 mm x 3 mmt) molded at a cylinder temperature of 260 °C and a mold temperature of 65 °C was measured using a tracking tester [YST-112, manufactured by Yamayo Testing Instruments] in accordance with ASTM D3638:2021. That is, a voltage of 300 V to 600 V was applied at 25 V intervals, a 0.1% aqueous solution of ammonium chloride was dropped every 30 seconds at each voltage, and the applied voltage at which tracking did not occur for 50 drops or more was calculated. An applied voltage of 600 V at which tracking did not occur was considered to be passed, and one less than 600 V was considered to be failed.

[0031] 3.Mold releasability Using an injection molding machine [ROBOSHOT α-S100iA manufactured by Fanuc], 2 mmt test pieces (50 mm x 90 mm x 2 mmt) were molded at a cylinder temperature of 260°C and a mold temperature of 65°C. If no cracks occurred in the molded product or sprue when it was released from the mold, it was marked as ◯, and if cracks occurred or release was difficult, it was marked as ×.

[0032] 4.Thermal stability Using an injection molding machine [ROBOSHOT α-S100iA manufactured by FANUC], the mold was left to dwell for 10 minutes at a cylinder temperature of 260°C and a mold temperature of 60°C, after which five 2mmt test pieces (50mm x 90mm x 2mmt) were molded. The silver in each of the five pieces was visually inspected and judged according to the following criteria. ○: The number of sheets with silver spots is 2 or less and the silver spots area is 200 mm2 or less on all molded products. 2 less than ×: The number of sheets with silver spots is 3 or more, or the area of ​​silver spots on any of the molded products is 200 mm 2 End

[0033] [Table 2]

[0034] As shown in Table 2, according to the present invention, it is possible to provide a flame-retardant insulating resin composition having excellent flame retardancy, tracking resistance, mold releasability and thermal stability. [Industrial Applicability]

[0035] Molded articles and sheets made of the insulating flame-retardant resin composition of the present invention can be used for various applications, such as automobile peripheral parts and battery peripheral members.

Claims

1. The insulating flame-retardant resin composition comprises 100 parts by weight of (A) a polycarbonate resin (component A) and 0.5 to 1.8 parts by weight of (B) a flame retardant (component B), the flame retardant being a nitrogen-containing compound.

2. 2. The insulating flame-retardant resin composition according to claim 1, wherein the nitrogen-containing compound is melamine cyanurate.

3. 3. The insulating flame-retardant resin composition according to claim 1, further comprising 0.05 to 1.8 parts by weight of (C) carbon black (component C) per 100 parts by weight of component A.

4. 3. The insulating flame-retardant resin composition according to claim 1, wherein the viscosity average molecular weight of component A is 17,000 to 25,500.

5. 3. The insulating flame-retardant resin composition according to claim 1, wherein component B is a nitrogen-containing compound having a ratio of particles having a particle size of 50 μm or more as measured by a microtrack method of less than 0.1%.

6. 3. A molded article or sheet obtained by molding the insulating flame-retardant resin composition according to claim 1 or 2.

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