JP2008150450A - Flame-retardant polycarbonate resin composition having improved fluidity - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having flame retardancy with excellent eco-friendliness compared with conventional flame-retardants and enabling remarkable improvement in the appearance and fluidity while keeping the excellent performance of a polycarbonate resin such as heat-resistance and thermal stability, and utilizable as a material for various large-sized or thin-walled molded articles and various flame-retardant industrial parts. <P>SOLUTION: The flame-retardant polycarbonate resin composition having improved fluidity is composed of (A) a polycarbonate resin, (B) a basic metal soap, (C) a silicone compound, (D) an organic metal salt compound and (E) a fiber-forming fluorine-containing polymer, wherein the basic metal soap B is composed of one or more saturated or unsaturated aliphatic monocarboxylic acids and magnesium or calcium, and the silicone compound C has a main chain having a branched structure and contains an organic functional group which contains an aromatic group as an essential component. The invention further provides a molded article made of the resin composition. <P>COPYRIGHT: (C)2008,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 both a high molecular weight and a low molecular weight, and using a polycarbonate resin branched to either (Patent Document 1), blending 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, in these techniques, the above-mentioned excellent characteristics of the polycarbonate resin are included. There is a problem that any one or more of them are greatly damaged, and the improvement has been strongly desired.
JP 2001-226576 A JP 2000-319497 A JP 2000-103951 A

Moreover, although the method (patent document 4) which improves fluidity | liquidity by mix | blending a fatty acid with polycarbonate resin is proposed, in this case, 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 For this improvement, a method of blending an organic acid and an amide compound in a polycarbonate resin has been proposed (Patent Document 5). However, although the reduction in mechanical strength has been improved, the appearance of the molded product is inferior ( There is a problem of occurrence of silver streak), and a polycarbonate resin composition having both high fluidity and good appearance has not been obtained.
JP 61-162520 A JP 2006-37032 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, but in order to meet safety requirements in the electrical, electronic, and OA fields, it is equivalent to UL94V-0, V-1, or even 5V. There is a demand for higher flame retardancy. 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 that improves the appearance and fluidity while maintaining the above-mentioned various performances, and has improved flame retardancy without using a flame retardant composed of halogen compounds such as bromine and chlorine. The purpose is to provide.

  As a result of intensive studies in view of such problems, the present inventors have formulated a specific amount of a specific basic metal soap, a silicone compound, an organometallic salt compound, and a fiber-forming fluorine-containing polymer into a polycarbonate resin. The present inventors have found that flame retardancy is imparted without impairing various excellent performances of the polycarbonate resin, and that the appearance and fluidity are specifically and significantly improved, thereby completing the present invention.

  That is, the present invention comprises 100 parts by weight of a polycarbonate resin (A), 0.2 to 1.5 parts by weight of a basic metal soap (B), 0.01 to 3 parts by weight of a silicone compound (C), an organometallic salt compound ( D) A resin composition comprising 0.01 to 0.3 parts by weight and a fiber-forming fluoropolymer (E) 0.05 to 5 parts by weight, wherein the basic metal soap (B) has 12 carbon atoms. A metal soap composed of one or more of -30 saturated or unsaturated aliphatic monocarboxylic acids and magnesium or calcium, and the silicone compound (C) has a branched structure and an organic functional group. It is characterized by containing an aromatic group as the organic functional group, and optionally containing a hydrocarbon group other than the aromatic group as the organic functional group other than the terminal group. Flame retardant poly with improved fluidity Boneto resin composition, and is intended to provide it from the consisting moldings.

  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, it is possible to improve the appearance and fluidity specifically and significantly while maintaining the excellent impact strength, heat resistance, thermal stability, etc. inherent to the polycarbonate resin. It can be used as a material for various flame-retardant industrial parts.

  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 basic metal soap (B) used in the present invention is a metal soap composed of one or more saturated or unsaturated aliphatic monocarboxylic acids having 12 to 30 carbon atoms and magnesium or calcium. . The aliphatic monocarboxylic acid may have a side chain or a functional group such as a hydroxyl group, a ketone group, an aldehyde group, and an epoxy group in its structure. Typical examples include caprylic acid, caproic acid, capric acid, Lauric acid, myristic acid, palmitic acid, stearic acid, alginate, heptadecyl acid, behenic acid, oleic acid, elaidic acid, erucic acid, linoleic acid, linolenic acid, ricinoleic acid, hydroxystearic acid, montanic acid, isostearic acid, epoxy Stearic acid is mentioned. Of these, behenic acid is preferably used.

  The basic metal soap (B) is produced by a known production method from one or more of the above aliphatic monocarboxylic acids and magnesium or calcium oxide or hydroxide, and its magnesium or calcium content Is a basic metal salt contained in an excess of 1 mol or less than the corresponding equivalent.

  The basic metal soap (B) used in the present invention includes basic magnesium stearate, basic calcium stearate, basic magnesium stearate, basic calcium stearate, basic magnesium behenate, basic behenate. Calcium behenate is preferably used among these.

  The compounding quantity of basic metal soap (B) is 0.2-1.5 weight part with respect to 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.2 parts by weight, the effect of improving the fluidity is inferior. More preferably, it is 0.3-1.2 weight part, More preferably, it is 0.4-1.0 weight part.

As the silicone compound (C) used in the present invention, as shown in the following general formula (1), the main chain has a branched structure and contains an aromatic group as an organic functional group. Group and a hydrocarbon group (excluding an aromatic group).
General formula (1)

  In the general formula (1), R1, R2 and R3 represent an organic functional group bonded to the main chain, and X represents a terminal group.

That is, it has a T unit (RSiO _1.5 ) and / or a Q unit (SiO _2.0 ) as a branch unit. These preferably contains more than 20 mol% of the total siloxane units _{(R 3~0 SiO 2~0.5).} (R represents an organic functional group.) Further, this silicone compound (C) has an aromatic group of 20 out of organic functional groups bonded to the main chain or branched side chain as a terminal group or a functional group other than the terminal group. It is preferably at least mol%.

  As this organic functional group, an aromatic group is essential. As this aromatic group, phenyl, biphenyl, naphthalene or a derivative thereof is preferable, but a phenyl group is more preferable.

  Of the organic functional groups in the silicone compound (C) attached to the main chain or branched side chain, the organic group other than the aromatic group is preferably a hydrocarbon group having 4 or less carbon atoms, and preferably a methyl group. Can be used. Furthermore, the terminal group is preferably one kind selected from methyl group, phenyl group and hydroxyl group, or a mixture of these two kinds to three kinds.

  The average molecular weight (weight average) of the silicone compound (C) is preferably 3000 to 500000, and more preferably 5000 to 270000.

The compounding quantity of a silicone compound (C) is 0.01-3 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is outside the range, the flame retardant effect is insufficient in any case, which is not preferable. More preferably, it is 0.03 to 1 part by weight.

   Examples of the organic metal salt compound (D) 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 (D) 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. On the other hand, if it exceeds 0.3 parts by weight, the problem that the mechanical strength is lowered 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 (E) 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 amount of the fiber-forming fluoropolymer (E) is 0.05 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). If the 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.

  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, mica, potassium titanate whisker, aluminum borate whisker, wollastonite powder, silica powder and the like.

  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)
Basic metal soap:
EC-700H (basic calcium behenate) manufactured by Eishin Kasei
(Hereinafter abbreviated as basic Ca soap)
Silicone compounds:
The silicone compound was produced according to a general production method. That is, a silicone compound partially condensed by dissolving an appropriate amount of diorganodichlorosilane, monoorganotrichlorosilane and tetrachlorosilane, or a partially hydrolyzed condensate thereof in an organic solvent, adding water and hydrolyzing. Then, triorganochlorosilane was added and reacted to terminate the polymerization, and then the solvent was separated by distillation or the like. The structural characteristics of the silicone compound synthesized by the above method are as follows:
・ D / T / Q unit ratio of main chain structure: 40/60/0 (molar ratio)
-Ratio of phenyl group in all organic functional groups (*): 60 mol%
-Terminal group: methyl group only-Weight average molecular weight (**): 15000
*: The phenyl group is first contained in the T unit in the silicone containing the T unit, and the remaining D group is contained in the D unit. When the phenyl group is attached to the D unit, the one attached is preferential, and when the phenyl group remains, two are attached. Except for the terminal group, the organic functional group is a methyl group except for the phenyl group.
**: Weight average molecular weight is two significant digits.
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)

  The above-mentioned various raw materials are collectively put in a tumbler at the blending ratios shown in Tables 2-3, and after dry mixing for 10 minutes, using a twin screw extruder (KTX37 manufactured by Kobe Steel), the melting temperature is 280 ° C. And kneaded to obtain pellets of the polycarbonate resin composition. Various test pieces were processed from the obtained pellets 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) Izod Impact Test A test piece for Izod impact test was processed under a melting temperature of 280 ° C., and Izod impact strength was measured according to ASTM D256. The measurement temperature is 23 ° C., and the thickness of the test piece is 3.2 mm. An impact value of 30 kg / cm / cm or more was considered acceptable.

(3) Heat resistance (deflection temperature under load: HDT)
A test piece for 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. The fiber stress was set to 18.5 Kg / cm ² and the measurement specimen was not annealed. The thickness of the test piece is 6.4 mm.

(4) Flame Retardancy Evaluation (I) UL94 / V Test After drying various pellets obtained at 125 ° C. for 4 hours, an injection molding machine (245 ° C., injection pressure 1600 kg / day using J-100SAII manufactured by Nippon Steel Works) A flame retardant test piece (125 × 13 × 2.0 mm) was molded at cm ^{2. 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%, and Underwriters Laboratories The flame retardancy was evaluated in accordance with the established UL94 / V test (flammability test of plastic materials for equipment parts), and the class according to UL94 / V is 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.

(II) UL94 / 5V test After various pellets obtained were dried at 125 ° C. for 4 hours, they were flame retardant at an injection molding machine (245 ° C., injection pressure 1600 kg / cm ² using J-100SAII manufactured by Nippon Steel Works). A strip-shaped test piece (125 × 13 × 2.0 mm) and a plate-shaped test piece (150 × 150 × 2.0 mm) for evaluation were molded, and the obtained test piece was left in a constant temperature room at 23 ° C. and 50% humidity for 72 hours, The flame retardancy was evaluated in accordance with the UL94 / 5V test (flammability test of plastic materials for equipment parts) defined by Underwriters Laboratories, and the classes according to UL94 / 5V are shown in Table 2.

５ＶＢ以上を合格とした。

5 VB or more was regarded as acceptable.

(5) Appearance Evaluation A flat plate test piece (50 × 90 × 3 mm) was prepared under a melting temperature of 320 ° C., and the presence or absence of silver streaks on the surface of the molded product was visually determined.

＊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 3, when the polycarbonate resin composition satisfied the constituent requirements of the present invention (Examples 1 to 6), the standard was satisfied over all evaluation items.

As shown in Table 4, when the polycarbonate resin composition did not satisfy the constituent requirements of the present invention, each case had some drawbacks.
Since the comparative example 1 was not mix | blended with basic Ca soap, it was inferior to fluidity | liquidity.
Comparative Example 2 was inferior in flame retardancy (V, 5V), impact strength and appearance because basic Ca soap was blended beyond the specified range.
Comparative Example 3 was inferior in flame retardancy (5 V) because the amount of Si was less than the specified range.
Comparative Example 4 was inferior in flame retardancy (V, 5V) because Si was blended beyond the specified range.
Comparative Example 5 was inferior in flame retardancy (V, 5V) because the amount of metal salt was less than the specified range.
Since Comparative Example 6 had less PTFE than the specified range, it was inferior in flame retardancy (V, 5V).

Claims (4)

  Polycarbonate resin (A) 100 parts by weight, basic metal soap (B) 0.2-1.5 parts by weight, silicone compound (C) 0.01-3 parts by weight, organometallic salt compound (D) 0.01- A resin composition comprising 0.3 part by weight and 0.05 to 5 parts by weight of a fiber-forming fluoropolymer (E), wherein the basic metal soap (B) is saturated or non-saturated with 12 to 30 carbon atoms. A metal soap composed of one or more saturated aliphatic monocarboxylic acids and magnesium or calcium, and the silicone compound (C) has a branched structure and an organic functional group, Improved fluidity characterized by containing an aromatic group as an essential organic functional group, and optionally containing a hydrocarbon group other than an aromatic group as an organic functional group other than a terminal group. Flame retardant polycarbonate resin composition .   The flame retardant having improved fluidity according to claim 1, wherein the blending amount of the basic metal soap (B) is 0.3 to 1.2 parts by weight per 100 parts by weight of the polycarbonate resin (A). Polycarbonate resin composition.   The flame-retardant polycarbonate resin composition with improved fluidity according to claim 1 or 2, wherein the basic metal soap (B) is basic calcium behenate.   A molded article formed from the flame-retardant polycarbonate resin composition having improved fluidity according to any one of claims 1 to 3.