JP2009030004A - Flowability improved, flame-retardant polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition which enables to improve specifically and remarkably the flame retardation and the flowability while maintaining such excellent performance of the impact strength, heat resistance and thermal stability as a polycarbonate resin has originally, and which is usable as various kinds of big sized- or thin walled-molded articles and a variety of flame-retardant industrial component materials. <P>SOLUTION: The flowability-improved, flame retardant polycarbonate resin composition is a resin composition consisting of 100 parts by weight of a polycarbonate resin (A), 2-12 parts by weight of a flow modifier (B), 0.01-0.3 part by weight of an organometallic salt compound (C), and 0.05-5 parts by weight of a fiber formation-type, fluorine-containing polymer (D), and if desired, a lamellar inorganic compound (E), with the flow modifier (B) being a copolymer of an aromatic vinyl-based monomer and a phenyl methacrylate; and the molded article is composed thereof. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition and a molded article formed therefrom. More specifically, the present invention provides a polycarbonate resin composition having improved appearance, fluidity and flame retardancy while maintaining the impact resistance, heat resistance, thermal stability, etc., which are the characteristics of polycarbonate resin, and a molded product thereof. It is.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, thermal stability, and the like, and is widely used in fields such as electricity, electronics, ITE, machinery, and automobiles. On the other hand, in addition to these excellent performances of the resin, in each of the aforementioned fields, a material having a high fluidity (moldability) is required in order to satisfy the design and design requirements. In particular, in recent years, the trend of weight reduction of products has been remarkable, and the actual situation is that the demand for improvement in fluidity of polycarbonate resins has become more prominent.

On the other hand, as techniques for improving the fluidity of the polycarbonate resin composition, various techniques have been proposed since the past, but all have advantages and disadvantages, and satisfactory materials are not necessarily proposed. For example, paying attention to the molecular weight of the polycarbonate resin, a method using a high molecular weight and a low molecular weight in combination, and using a polycarbonate resin branched to either (Patent Document 1), blending an ABS resin or MBS resin in the polycarbonate resin (Patent Document 2) or a method of blending an ABS resin or a phosphate ester with a polycarbonate resin (Patent Document 3) has been proposed. However, these techniques include the above-mentioned excellent characteristics of the polycarbonate resin. There is a problem that any one or more of them are greatly damaged, and there has been a strong demand for improvement.
Moreover, although the method (patent document 4) which improves a fluidity | liquidity by mix | blending a fatty acid with polycarbonate resin is proposed, although fluidity | liquidity improves, decomposition | disassembly of polycarbonate resin by a fatty acid occurs and mechanical strength is improved. There were fundamental problems such as incurring a decrease in

JP 2001-226576 A JP 2000-319497 A JP 2000-103951 A JP 61-162520 A

  In addition to fluidity, there are many parts that require high flame resistance (UL94V) and impact resistance, such as personal computer exterior parts, in the fields of electrical, electronic, and OA. Polycarbonate resin is a highly flame-retardant plastic material with self-extinguishing properties. However, in order to meet safety requirements in the electric, electronic, and OA fields, it has higher flame resistance equivalent to UL94V-0 and V-1. Is required. Therefore, in order to improve the flame retardancy of the polycarbonate resin, conventionally, a method of blending a halogen compound or a phosphorus compound as a flame retardant has been adopted. Among these, particularly for halogen compounds such as bromine and chlorine, it is desired to use a flame retardant that does not contain them from the environmental viewpoint.

  As described above, the conventional technology improves the fluidity at the expense of one or more of the excellent characteristics inherent in polycarbonate resin, such as impact resistance, heat resistance, and thermal stability. there were. The present invention provides a polycarbonate resin composition having improved fluidity while maintaining the above-mentioned various performances and having improved flame retardancy without using a flame retardant composed of halogen compounds such as bromine and chlorine. For the purpose.

  As a result of intensive studies in view of such problems, the present inventors have found that a specific flow modifier, an organometallic salt compound, a fiber-forming fluorine-containing polymer, and a plate-like inorganic compound depending on necessity, in polycarbonate resin By blending a specific amount, flame retardant properties are imparted without impairing various excellent performances of the polycarbonate resin, and the fluidity is specifically and significantly improved to complete the present invention. It came to.

  That is, the first aspect of the present invention comprises 100 parts by weight of a polycarbonate resin (A), 2 to 12 parts by weight of a fluidity improver (B), 0.01 to 0.3 parts by weight of an organometallic salt compound (C) and A resin composition comprising 0.05 to 5 parts by weight of a fiber-forming fluorine-containing polymer (D), wherein the fluidity improver (B) is a copolymer of an aromatic vinyl monomer and phenyl methacrylate It is intended to provide a flame retardant polycarbonate resin composition with improved fluidity, and a molded article comprising the same.

  The second aspect of the present invention is a polycarbonate resin (A) 100 parts by weight, a fluidity improver (B) 2-12 parts by weight, an organometallic salt compound (C) 0.01-0.3 parts by weight, A resin composition comprising 0.05 to 5 parts by weight of a fiber-forming fluoropolymer (D) and 2 to 25 parts by weight of a plate-like inorganic compound (E), wherein the fluidity improver (B) is aromatic The present invention provides a flame-retardant polycarbonate resin composition with improved fluidity, which is a copolymer of a vinyl monomer and phenyl methacrylate, and a molded article comprising the same.

  The flame retardant polycarbonate resin composition of the present invention has excellent flame retardancy without using a conventional flame retardant containing halogen, phosphorus or the like. For this reason, there is no concern about generation of a gas containing halogen or phosphorus due to the flame retardant during combustion, and the environment is excellent. Furthermore, since the fluidity can be improved specifically and significantly while maintaining the excellent impact strength, heat resistance, thermal stability, etc. inherent to the polycarbonate resin, various large or thin molded products, It can be used as various flame retardant industrial component materials.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  Although there is no restriction | limiting in particular in the viscosity average molecular weight of polycarbonate resin (A), Usually, it is 10,000-100000, More preferably, it is 15000-30000, More preferably, it is the range of 17000-26000 from the surface of moldability and intensity | strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

  The fluidity improver (B) used in the present invention is a copolymer of an aromatic vinyl monomer and phenyl methacrylate. Examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-tert. Butyl styrene etc. are mentioned, These can be used individually or in mixture of 2 or more types. Preferable fluidity improvers (B) include a styrene / phenyl methacrylate copolymer or a styrene / α-methylstyrene / phenyl methacrylate copolymer.

  Examples of the polymerization method of the fluidity improver (B) include emulsion polymerization, suspension polymerization, and bulk polymerization, and emulsion polymerization is particularly preferably used.

  The fluidity improver (B) is commercially available, and includes Metablene TP003 manufactured by Mitsubishi Rayon Co., Ltd.

  The compounding quantity of a fluid improvement agent (B) is 2-12 weight part with respect to 100 weight part of polycarbonate resin (A). If the blending amount is less than 2 parts by weight, the effect of improving the fluidity is inferior. More preferably, it is 3-10 weight part, More preferably, it is 4-8 weight part.

   Examples of the organic metal salt compound (C) used in the present invention include aromatic sulfonic acid metal salts and perfluoroalkanesulfonic acid metal salts. Examples of the metal include alkali metals and alkaline earth metals. Preferably, potassium salt of 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, paratoluenesulfonic acid Sodium, perfluorobutanesulfonic acid potassium salt and the like can be used.

  The compounding amount of the organometallic salt compound (C) is 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the flame retardancy is lowered, which is not preferable. Moreover, when it exceeds 0.3 weight part, since the problem that a flame retardance falls will generate | occur | produce, it is not preferable. Preferably it is 0.02-0.2 weight part, More preferably, it is 0.02-0.1 weight part.

  As the fiber-forming fluorine-containing polymer (D) used in the present invention, those that form a fiber structure (fibril structure) in the polycarbonate resin (A) are preferable. Polytetrafluoroethylene, tetrafluoroethylene Examples thereof include a system copolymer (for example, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), a partially fluorinated polymer as shown in US Pat. No. 4,379,910, a polycarbonate produced from a fluorinated diphenol, and the like. In particular, polytetrafluoroethylene having a molecular weight of 1,000,000 or more and a fibril-forming ability having a secondary particle diameter of 100 μm or more is preferably used.

  The blending amount of the fiber-forming fluoropolymer (D) is 0.05 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.05 parts by weight, the effect of preventing dripping during combustion is inferior, which is not preferable. On the other hand, if the amount exceeds 5 parts by weight, granulation becomes difficult, which hinders stable production. This amount is preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 part by weight. In this range, the balance between flame retardancy and moldability is further improved.

  Examples of the plate-like inorganic compound (E) used in the present invention include mica. Mica is a silicate mineral and includes muscovite, biotite, phlogopite, artificial phlogopite, etc. The shape is flaky. Of these, mica, which is widely used as a resin filler for the purpose of reinforcing rigidity and reducing warpage, is preferably used. When these are used in combination with the organometallic salt compound (C) of the present invention and the fiber-forming fluorine-containing polymer (D), they are also effective in specifically reducing the combustion time.

  The compounding quantity of a plate-shaped inorganic compound (E) is 2-25 weight part with respect to 100 weight part of polycarbonate resin (A). If it is less than 2 parts by weight, the effect of improving the flame retardancy is not sufficient, and if it exceeds 25 parts by weight, the flame retardancy is inferior. More preferably, it is in the range of 5 to 15 parts by weight. In this range, the flame retardancy is further improved.

  There are no particular limitations on the method of blending the various blending components (A), (B), (C), (D), and (E) of the present invention, and any mixer, for example, a tumbler, ribbon blender, high-speed mixer, etc. These can be mixed and melt-kneaded easily with a normal single-screw or twin-screw extruder. Moreover, there is no restriction | limiting in particular also about these compounding orders.

  In addition, other known additives such as mold release agents, ultraviolet absorbers, fillers, antistatic agents, antioxidants, phosphorus-based heat stabilizers, dyes and pigments, and additives (when epoxy is used) may be added at the time of mixing. Bean oil, liquid paraffin, and the like).

  Examples of the filler include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, potassium titanate whisker, aluminum borate whisker, wollastonite powder, and silica powder.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise noted, based on weight standards.

The details of the used blending components are as follows.
Polycarbonate resin:
Caliber 200-20 (viscosity average molecular weight: 19000) manufactured by Sumitomo Dow
(Hereafter abbreviated as PC)
Fluidity improver:
Styrene / phenyl methacrylate copolymer TP003 manufactured by Mitsubishi Rayon Co., Ltd. (hereinafter abbreviated as fluidity improver)
Organometallic salt compounds:
Sodium paratoluenesulfonate (hereinafter abbreviated as metal salt)
Fiber-forming fluorine-containing polymer:
NEOFRON FA500 (polytetrafluoroethylene) manufactured by Daikin Industries, Ltd.
(Hereafter abbreviated as PTFE)
Plate-like inorganic compounds:
A41 manufactured by Yamaguchi Mica Industry (hereinafter abbreviated as mica)

  The above-mentioned various raw materials are collectively put into a tumbler at the blending ratios shown in Tables 2 to 4, and after dry mixing for 10 minutes, using a twin screw extruder (KTX37 manufactured by Kobe Steel) to a melting temperature of 280 ° C. And kneaded to obtain pellets of the polycarbonate resin composition. From the obtained pellets, various test pieces were processed using an injection molding machine (J100E-C5 manufactured by Nippon Steel Works), and various data were collected by the following methods.

(1) Archimedes spiral flow fluidity The flow length at a channel thickness of 1 mm was measured using an Archimedes spiral flow mold under the conditions of a melting temperature of 280 ° C. and an injection pressure of 1600 kg / cm ² . A flow length of 140 mm or more was regarded as acceptable.

(2) Heat resistance (deflection temperature under load: HDT)
A test piece for a heat resistance test was processed under a melting temperature of 280 ° C., and a deflection temperature under load (HDT) was measured in accordance with ASTM D648. Fiber Stress was set at 18.5 kg / cm ^2, the annealing treatment of test piece for measurement was not carried out. The thickness of the test piece is 6.4 mm. HDT passed 130 degreeC or more as the pass.

(3) Evaluation of granulating properties The granulating properties were determined by visually observing the state of the strands during granulation and determining good / bad.

(4) Evaluation of flame retardancy After the various pellets obtained were dried at 125 ° C. for 4 hours, flame retardant at an injection molding machine (245 ° C., injection pressure 1600 kg / cm ² using J-100SAII manufactured by Nippon Steel) An evaluation test piece (125 × 13 × 3.0 mm or 125 × 13 × 1.5 mm) was molded, and the obtained test piece was allowed to stand for 72 hours in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50%, as defined by Underwriters Laboratories. The flame retardancy was evaluated according to the UL94 test (flammability test of plastic materials for equipment parts), and the classes according to UL94 are shown in Table 1.

残炎時間とは、着火源を遠ざけた後の試験片が、有炎燃焼を続ける時間の長さであり、ドリップによる綿の着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火されるかどうかによって決定される。Ｖ−１以上を合格とした。

The after flame time is the length of time that the test piece after the ignition source is moved away from the flame, and the ignition of the cotton by the drip is for the sign about 300 mm below the lower end of the test piece. Of cotton is ignited by a drip from the specimen. V-1 or higher was accepted.

＊ＮＲ：Ｎｏ Ｒａｔｉｎｇの略。Ｖ−０、Ｖ−１、Ｖ−２に属さない。

* NR: Abbreviation for No Rating. It does not belong to V-0, V-1, or V-2.

  As shown in Table 2, when the polycarbonate resin composition satisfied the constituent requirements of the present invention (Examples 1 to 6), good results were shown over all the evaluation items.

On the other hand, as shown in Table 3, when the polycarbonate resin composition did not satisfy the constituent requirements of the present invention, each case had some drawbacks.
Since the fluidity improver was not mix | blended with the comparative example 1, it was inferior to fluidity | liquidity.
In Comparative Example 2, the fluidity improver was less than the specified amount, and the fluidity was poor.
In Comparative Example 3, the amount of the metal salt was less than the specified amount, and the flame retardancy was poor.
Comparative Example 4 was a case where the metal salt was more than the specified amount and was inferior in flame retardancy.
Comparative Example 5 was a case where the blending amount of PTFE was less than the specified amount and was inferior in flame retardancy.
Comparative Example 6 was a case where PTFE was more than the specified amount, and was inferior in flame retardancy and granulation properties.
Comparative Example 7 was a case where the fluidity improver was more than the specified amount and was inferior in flame retardancy, heat resistance and granulation properties.

As shown in Examples 7 to 9 of Table 4, when the polycarbonate resin composition did not satisfy the constituent requirements of the present invention, each case had some drawbacks.
In Comparative Examples 8 and 9, the amount of mica was greater than the specified amount, and the flame retardancy at a thickness of 1.5 mm was inferior.

Claims (6)

  100 parts by weight of the polycarbonate resin (A), 2 to 12 parts by weight of the fluidity improver (B), 0.01 to 0.3 parts by weight of the organometallic salt compound (C) and the fiber-forming fluorine-containing polymer (D) 0 0.05-5 parts by weight of a resin composition, wherein the fluidity improver (B) is a copolymer of an aromatic vinyl monomer and phenyl methacrylate Flame retardant polycarbonate resin composition.   100 parts by weight of the polycarbonate resin (A), 2 to 12 parts by weight of the fluidity improver (B), 0.01 to 0.3 parts by weight of the organometallic salt compound (C), and the fiber-forming fluorine-containing polymer (D) 0 A resin composition comprising 0.05 to 5 parts by weight and 2 to 25 parts by weight of a plate-like inorganic compound (E), wherein the fluidity improver (B) is a co-polymer of an aromatic vinyl monomer and phenyl methacrylate. A flame-retardant polycarbonate resin composition having improved fluidity, which is a polymer.   The flame retardant polycarbonate having improved fluidity according to claim 1 or 2, wherein the fluidity improver (B) is a styrene / phenyl methacrylate copolymer or a styrene / α-methylstyrene / phenyl methacrylate copolymer. Resin composition.   The difficulty in improving fluidity according to claim 1 or 2, wherein the blending amount of the fluidity improver (B) is 3 to 10 parts by weight per 100 parts by weight of the polycarbonate resin (A). Flammable polycarbonate resin composition.   The flame-retardant polycarbonate resin composition having improved fluidity according to claim 2, wherein the plate-like inorganic compound (E) is mica.   A molded article formed from the flame retardant polycarbonate resin composition having improved fluidity according to any one of claims 1 to 5.