JP2005171241A - Polycarbonate-based resin composition having long-durable antistatic properties, and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic polycarbonate-based resin composition that has excellent permanent antistatic properties, mechanical properties including impact resistance, and molding processability, and does not show delamination. <P>SOLUTION: This long-durable antistatic polycarbonate-based resin composition comprises 10-98 wt.% of (A) an aromatic polycarbonate-based resin, 1-30 wt.% of (B) a long-durable antistatic agent, 1-30 wt.% of (C) phosphor-containing flame retardant, and 0-30 wt.% of (D) a fluorine-containing compound, based on 100 wt.% of the total of (A) to (D), and satisfies V-2 in the UL Standards 94V testing. This composition may also contain more than 0 wt.% and not more than 40 wt.% of (E) an inorganic filler. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an antistatic polycarbonate resin composition and a molded article molded from the composition.
More specifically, by including a specific amount of phosphorus flame retardant and fluorine compound, UL standard 94 polycarbonate and antistatic material can be processed in a temperature range where decomposition is difficult, and long-term stable and stable charging. The present invention relates to a resin composition excellent in mechanical properties, slidability, and flame retardancy capable of exhibiting prevention ability, and a molded product molded from the composition.

  Conventionally, polycarbonate-based resins have been frequently used for the exterior and internal mechanism parts of optical disks and magnetic disks for recording data, music, video, and the like. With recent increases in density and capacity, plastics with some antistatic properties are starting to be used.

However, none of the polycarbonate resins has been given antistatic properties. For this reason, general-purpose plastics such as ABS or PC / ABS accounted for many applications that require such antistatic performance, but the addition of antistatic materials provides sufficient antistatic properties. Impact resistance and elastic modulus were not sufficient.

  In addition, when an antistatic material is added, a halogen-based flame retardant must be used to achieve flame retardancy, and further, there is a problem that sliding wear and flame retardancy are remarkably lowered.

  Therefore, there is a need for a technique for imparting antistatic properties while maintaining the excellent toughness and rigidity of polycarbonate resin.

As a resin composition having antistatic properties and excellent mechanical properties such as impact resistance and molding processability, Japanese Patent No. 2565846 (Patent Document 1) discloses a method for producing an antistatic material, polycarbonate, aromatic A composition comprising a modified vinyl polymer to which an aromatic vinyl monomer, a monomer of styrene or an acrylate ester is added, and a rubbery polymer obtained by graft-modifying an aromatic vinyl monomer or the like Japanese Patent Publication No. 5-24175 (Patent Document 2) discloses a modified vinyl-based heavy polymer to which a polyether ester amide, a polycarbonate, an aromatic vinyl monomer, a monomer of styrene or an acrylate ester is added. A composition containing a rubbery polymer obtained by graft-modifying a polymer and an aromatic vinyl monomer has been proposed.
However, when an antistatic material is applied at the processing temperature level of the polycarbonate resin, the antistatic material is decomposed, and sufficient mechanical properties cannot be obtained.
In addition, JP-A-11-1997767 (Patent Document 3) discloses that an aromatic polycarbonate resin is added to a polyether ester amide, a phosphate ester, talc, mica, glass flakes, wax, without using a halogen flame retardant. Disclosed is a resin composition comprising an inorganic filler selected from lathnite, a rubbery polymer, and polytetrafluoroethylene having a fibril-forming ability, and the composition has flame retardancy, heat resistance, impact resistance and appearance. It is disclosed that it is excellent.
Japanese Patent No. 2565846 Japanese Patent Publication No. 5-24175 JP-A-11-1997767

  In those disclosed in Patent Documents 1 and 2, the melt viscosity during processing is lowered to maintain the mechanical properties, but the impact strength at the polycarbonate level has not been obtained.

  There has been a demand for a resin composition having high impact characteristics, elastic modulus, and slidability, such as polycarbonate, and further having antistatic properties and flame retardancy with a non-halogen flame retardant.

  Note that many of the conventionally known high molecular weight type antistatic materials are elastomeric and are themselves soft, and even if added to a polycarbonate resin, there is a problem that the sliding wear resistance performance is lowered. there were.

  As in Patent Document 3, attempts have been made to achieve a long-lasting antistatic property with a flame retardant having a low environmental load only with a polycarbonate-based resin, but polytetrafluoroethylene having a fibril forming ability to be used in combination. However, although high flame retardancy can be obtained, it has been difficult to suppress deterioration of sliding characteristics due to addition of an antistatic material.

As a result of sincere consideration to solve the above problems, the present inventor considered the above problems by combining a polycarbonate resin, a phosphate ester flame retardant, and an antistatic material without including an ABS resin or the like. It is possible to obtain a polycarbonate resin composition having sustained antistatic properties satisfying V-2 in the UL standard 94V test while suppressing decomposition caused by the thermal stability and maintaining stable sliding characteristics. I found it. Furthermore, it has been found that a more stable antistatic property can be obtained by adding an inorganic filler.

That is, the polycarbonate-type resin composition concerning this invention and its use are roughly shown below.
(1) (A) aromatic polycarbonate resin, (B) persistent antistatic material, (C) phosphorus flame retardant, (D) fluorine compound, and the total of (A) to (D) is 100 When weight%
(A) Aromatic polycarbonate resin: 10 to 98% by weight,
(B) Persistent antistatic material: 1 to 30% by weight,
(C) Phosphorus flame retardant: 1 to 30% by weight,
(D) Fluorine compound: 0 to 30% by weight,
A long-lasting antistatic polycarbonate resin composition satisfying V-2 in the UL standard 94V test including
(2) (A) Aromatic polycarbonate resin, (B) antistatic material, (C) phosphorus flame retardant, (D) fluorine compound, and the total of (A) to (D) is 100 weights %
(A) Aromatic polycarbonate resin: 10 to 98% by weight,
(B) Persistent antistatic material: 1 to 30% by weight,
(C) Phosphorus flame retardant: 1 to 30% by weight
(D) fluorinated compound: in the range of 0 to 30% by weight,
And when the total of (A) to (D) is 100% by weight,
(E) V-2 in UL standard 94V test containing inorganic filler in an amount of more than 0 and not more than 40% by weight
A durable antistatic polycarbonate resin composition satisfying
(3) (B) Persistent antistatic materials are polyether esters, polyethylene glycol polyamides or polyester amides, polyethylene glycol methacrylate copolymers, poly (ethylene oxide / propylene oxide) copolymers, poly (epi (Chlorohydrin / ethylene oxide) copolymers, quaternary ammonium base-containing methacrylate copolymers, and high molecular weight polyethylene glycols, and at least one selected from resins classified as long-lasting electrically conductive resins.
(4) (C) The phosphorus flame retardant is at least one selected from phosphate ester flame retardants.
(5) (D) The fluorine compound contains a polytetrafluoroethylene resin having a molecular weight of 3 million to 10 million having sliding wear.
(6) (E) Inorganic filler is talc, mica, barium sulfate, glass fiber, hollow glass fiber, carbon fiber, hollow carbon fiber, titanium oxide whisker, fibrous wollastonite, clay, silica, glass flake, glass At least one selected from beads and hollow fillers.
(7) The resin composition does not substantially contain a styrene butadiene acrylonitrile (ABS) resin component.
(8) The fluorine-based compound does not have a fibril forming ability.
(9) A molded article comprising the resin composition.
(10) External or internal mechanism plastics parts of optical disks, magnetic disks, electronic and electrical equipment, household equipment, or OA equipment on which the molded product records data, information, music, video, and the like.

According to the present invention, since it has a specific resin-additive composition, it has excellent mechanical properties such as long-lasting antistatic properties, impact resistance, and molding processability, and is capable of delamination (thousand turnover). An antistatic polycarbonate resin composition is obtained. Such a composition is suitably used as an exterior or internal mechanism plastic part for optical disks, magnetic disks, electronic and electrical equipment, household equipment, or OA equipment.

[(A) Polycarbonate resin]
The polycarbonate resin used in the present invention is produced by a known phosgene method or a melting method (for example, see Japanese Patent Laid-Open Nos. 63-15563 and 2-124934). It is. A copolymer polycarbonate can also be used. A plurality of polycarbonates can be used in combination. Furthermore, the terminal of the polycarbonate to be used may be sealed with any known terminal sealing agent. In the present invention, aliphatic, aromatic and aliphatic aromatic polycarbonates can be used, but aromatic polycarbonates are preferably used.

As the aromatic polycarbonate used in the present invention, the following formula (I) and the following formula (II)
And those having a structural unit represented by

(In the above formula, R ¹ and R ² are each independently a halogen atom or a monovalent hydrocarbon group, and B is — (R—) C (—R ′) — wherein R and R ′ Are each independently a hydrogen atom or a monovalent hydrocarbon group.], -C (= R ")-[where R" is a divalent hydrocarbon group], -O-, -S. —, —SO— or —SO ₂ —, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, a halide thereof, or a halogen atom, and p, q, and r are each independently 0-4. (It is an integer.)
The structural unit represented by the above formula (I) is composed of a diphenol component and a carbonate component. The diphenol that can be used to introduce the diphenol component is shown in the following formula (III).

(In the above formula, R ¹ , R ² , B, p and q are as defined above.)
Examples of the diphenol used in the present invention include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) propane (so-called Bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy- Bis (hydroxyaryl) alkanes such as 1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane; Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphe Dihydroxy aryl ethers such as 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, etc. Dihydroxydiaryl sulfides; 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone, 4,4′- Examples thereof include, but are not limited to, dihydroxydiaryl sulfones such as dihydroxy-3,3′-dimethyldiphenyl sulfone. Moreover, these compounds can also be used 1 type or in combination of 2 or more types. Of these, the use of 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

  Examples of the precursor for introducing the carbonate component include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, and dimethyl carbonate. , Carbonic acid diesters such as dibutyl carbonate and dicyclohexyl carbonate, and halogenated carbonyl compounds such as phosgene. Moreover, these compounds can also be used 1 type or in combination of 2 or more types. Among these, the use of diphenyl carbonate is particularly preferable.

  Next, the structural unit represented by the above formula (II) comprises a diphenol component, a resorcin and / or substituted resorcin component, and a carbonate component. For the introduction of the diphenol component, the same diphenol as described above can be used. Moreover, as a carbonate component, said carbonic acid diester or phosgene can be used. Furthermore, in order to introduce resorcin and / or substituted resorcin components, the following formula (IV):

(Here, R ³ and r are as defined above.)
These compounds can be used alone or in combination of two or more. Examples of such compounds include resorcin, and 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, Examples thereof include substituted resorcins such as 2,3,4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin, and the like. Of these, the use of resorcin is particularly preferred.

The weight average molecular weight of the polycarbonate is usually 10,000 to 100,000, preferably 18,000 to 40,000. The weight average molecular weight here is measured by GPC (gel permeation chromatography) using polystyrene corrected for polycarbonate. (It is also preferred that the intrinsic viscosity measured at 25 ° C. in methylene chloride is 0.35 to 0.65 dl / g.)
[(B) Sustainable antistatic material]
Examples of the antistatic material used in the present invention include polymeric antistatic materials.

Polymer type antistatic materials include polyoxyethylene glycol methacrylate copolymer, polyethylene glycol methacrylate copolymer, polyether amide, polyethylene glycol-based polyamide, polyether ester amide, polyether amide imide, poly (ethylene oxide / propylene oxide) And polyalkylene oxide copolymers such as copolymers, polyethylene oxide / epichlorohydrin copolymers, polyether esters, polybutylene terephthalate ionomer, polyethylene terephthalate ionomer, and quaternary ammonium base-containing methacrylate copolymers.

  Among these, polyether esters, polyethylene glycol polyamides, polyester amides, polyether ester amides, polyethylene glycol methacrylate copolymers, poly (ethylene oxide / propylene oxide) copolymers, poly (epichlorohydrin) / Ethylene oxide) copolymers, quaternary ammonium base-containing methacrylate copolymers, high molecular weight polyethylene glycols and the like are suitable.

Furthermore, as the polyether ester amide, a polyamide component having a number average molecular weight of 500 to 5,000 having carboxyl groups at both ends, a polyethylene glycol having a number average molecular weight of 300 to 4,000 and / or a number average molecular weight of 300 to 4 are used. Those derived from ethylene oxide adducts of 1,000 bisphenols are suitable, and by using these, good antistatic properties, flame retardancy and heat resistance can be imparted to the composition.
The polyamide component is (1) a lactam ring-opening polymer, (2) a polycondensate of aminocarboxylic acid, or (3) a polycondensate of dicarboxylic acid and diamine, and the lactam of (1) includes caprolactam, And enantolactam, capryl lactam, laurolactam, and the like. Examples of the aminocarboxylic acid (2) include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 1,1-aminoundecanoic acid, and 1,2- Examples include aminododecanoic acid. Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, isophthalic acid, and the diamine (3) includes hexamethylenediamine, heptamethylenediamine, and octamethylene. Examples thereof include diamine and decamethylenediamine. Of these, caprolactam, 12-aminododecanoic acid and adipic acid-hexamethylenediamine are preferably used, and caprolactam is more preferable.
Examples of bisphenols in the ethylene oxide adduct of bisphenols include bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, and 2,2-bis (4-hydroxyphenyl) butane. Of these, bisphenol A is preferred. It can be obtained by adding ethylene oxide to these bisphenols by a conventional method. Further, other alkylene oxides (propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, etc.) may be added together with ethylene oxide.
Unlike the principle that the low molecular weight antistatic material that has been used in the past bleeds out on the plastic surface and develops antistatic properties, such a durable antistatic material is alloyed on the surface layer and the core portion, and is electrically conductive. It is thought that the antistatic performance with excellent sustainability is exhibited because the network of the conductive polymer is formed.
The long-lasting antistatic material is not a low molecular weight material such as a surfactant, but has a polymer structure, and is exposed to a high temperature and high humidity for a long period of time. Even if it carries out, it has the characteristic that a charging characteristic can be maintained. Sustained antistatic measures are antistatic properties with respect to time. For example, a test piece is placed in a high-temperature and high-humidity environment at 85 ° C and 85%, and the surface resistance value and half-life after 2000 hours are evaluated. Those having these numerical values that do not vary substantially are the persistent antistatic materials used in the present invention.
[(C) Phosphorus flame retardant]
As the phosphorus flame retardant, a phosphate ester flame retardant exhibiting a plasticizer effect is used. It is important that the acid value of the phosphate ester is 1 or less, preferably 0.5 or less, more preferably 0.2 or less, and still more preferably 0.1 or less.

  As the phosphoric ester compound, the following formula (a)

^{(Wherein, R 1, R 2, R} 3 and R ⁴ are, each independently, represent a hydrogen atom or an organic group, R ¹
Except when = R ² = R ³ = R ⁴ = H. X represents a divalent or higher valent organic group, p is 0 or 1, q represents an integer of 1 or more, for example, an integer of 30 or less, and r represents an integer of 0 or more. ). However, it is not limited to these.

  In the above formula (a), examples of the organic group include an alkyl group, a cycloalkyl group, and an aryl group that may or may not be substituted. In addition, when substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group, and the like. A combined group (for example, an arylalkoxyalkyl group) or a group in which these substituents are combined by an oxygen atom, a sulfur atom, a nitrogen atom, or the like (for example, an arylsulfonylaryl group) may be used as the substituent. Good. The divalent or higher organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group. Examples include alkylene groups, and preferably (substituted) phenylene groups, polynuclear phenols such as those derived from bisphenols, and the relative positions of the two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p′-dihydroxydiphenylsulfone, bisphenol A, bisphenol S, dihydroxynaphthalene and the like.

Examples of specific phosphate ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, Diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) ) Phosphate,
Bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl diphosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyl diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl diphosphate, hydroquinone tetraxyl diphosphate, R ¹ to R ⁴ is alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy an is at a bisphenol a bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene phosphate, etc. Is mentioned. Preferably, triphenyl phosphate and various bisphosphates are used.

In addition to the above, a silicone flame retardant and a metal salt flame retardant may be included.
[(D) Fluorine compound]
Component (D) is a fluorine-based compound that improves the sliding wear of the resin composition, and such a fluorine compound can be used without particular limitation as long as it can improve the sliding wear. Specifically, a fluororesin is used.

  As the fluororesin, polytetrafluoroethylene is preferable. In particular, polytetrafluoroethylene having a weight average molecular weight of 3 million or more and 10 million or less is preferable. Since the fluororesin in the molecular weight range does not have a fibril forming ability, the sliding wear can be improved.

  Commercial products that can be used as such PTFE include: Argoflon manufactured by Ikuni Montedison, Teflon (registered trademark) manufactured by DuPont, full-on manufactured by ICI UK: Polyflon manufactured by Daikin Industries, Ltd. Is mentioned.

  Moreover, it is also possible to use a polymer obtained by polymerizing α-fluoroacrylic acid fluoroacrylic as an essential component as a fluorine-based resin. Specifically, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, Polyamideimide, polyetherimide, polyetheretherketone, polyimide, polyethernitrile, aromatic polyester and the like are polymerized with α-fluoroacrylic acid fluoroacryl.

Furthermore, in the present invention, a polyacetal resin obtained by graft polymerization of a fluoropolymer such as polytetrafluoroethylene, polyvinylidene fluoride, or polyvinyl fluoride can also be used as the fluororesin.
In the present invention, a fluororesin having no fibril forming ability is preferred. Polytetrafluoroethylene having fibril-forming ability has high flame retardancy, but has low sliding reforming performance.

Although the reason is not clear, it is considered that polytetrafluoroethylene having no fibril-forming ability forms fibrils by shearing at the time of molding or the like, and the slidability is lowered. In contrast, polytetrafluoroethylene, which does not have fibril-forming ability, does not form fibrils during molding processing, and dissolves uniformly during processing, so it is considered to have excellent slidability. The
[(E) Inorganic filler]
Known inorganic fillers such as fibrous fillers and non-fibrous fillers can be used without particular limitation. Specifically, talc, mica, barium sulfate, glass fiber, hollow glass fiber, carbon fiber, hollow carbon fiber, titanium oxide whisker, fibrous wollastonite, clay, silica, glass flakes, glass beads, and hollow filler are selected. At least one kind is used.

The composition according to the present invention comprises (A) an aromatic polycarbonate resin, (B) a persistent antistatic material, (C) a phosphorus flame retardant, (D) a fluorine compound, and (A) to (D ) Is 100% by weight,
(A) Aromatic polycarbonate resin: 10 to 98% by weight,
(B) Persistent antistatic material: 1 to 30% by weight,
(C) Phosphorus flame retardant: 1 to 30% by weight,
(D) Fluorine compound: 0 to 30% by weight,
In the amount of.

(B) The desirable addition amount of the long-lasting antistatic material is 3 to 25% by weight, and more desirably 5 to 20% by weight in order to prevent the problem of delamination while providing sufficient antistatic performance. In the present invention, since the above-described antistatic material is used in the above amount, delamination can be suppressed. In addition, as factors causing delamination, the amount of antistatic material added and the compatibility between the antistatic material and the polycarbonate resin are considered. However, the antistatic material described above has a compatibility with the polycarbonate resin. If the addition amount is as described above, delamination can be suppressed.
In addition, the antistatic property can be maintained within the above range of addition amount.
Specifically, even if the surface specific resistance value and the half-life characteristic are maintained in a high-temperature and high-humidity environment of 85 ° C. and 85% humidity, they are at a level that maintains the same numerical value even after 2000 hours. When conventional antistatic materials are used, it is often difficult to maintain antistatic properties in a high temperature and high humidity environment.

  (C) A desirable addition amount of the flame retardant is 3 to 25% by weight, and more desirably 3 to 20% by weight. If it is this range, the plasticizer effect will fully be exhibited with sufficient flame retardance.

  (D) A desirable addition amount of the fluorine-based compound may be contained in an amount of more than 0 and 30% by weight or less, more preferably 1.5 to 25% by weight, and still more preferably It is desirable that it is 2 to 20% by weight. Within this range, a sliding wear composition can be obtained (in this case, the amount of (A) is less than 98% by weight).

  The resin composition according to the present invention may further contain (E) an inorganic filler in an amount of more than 0 and not more than 40% by weight when the total of (A) to (D) is 100% by weight. . More preferably, the inorganic filler is contained in an amount of 1 to 30% by weight.

Thus, when the inorganic filler is included, the antistatic effect is stabilized although the reason is not clear as compared with the case where the inorganic filler is not included. If it is within the above range, the effect is manifested.
Further, if necessary, the composition may optionally contain at least one selected from low molecular weight polyolefin, silicone oil, and silicone resin fine particles as a sliding property improving agent. Any one of these may be selected, or two or more may be selected in combination. As the low molecular weight polyolefin, a polyolefin having a molecular weight of 10,000 or less is preferable. Examples of the polyolefin include polyethylene and polypropylene, and polyethylene is preferable. Polyethylene having a molecular weight of 10,000 or less is particularly preferred.
Although there is no restriction | limiting in particular as a silicone oil, For example, a dimethyl silicone oil, a methylphenyl silicone oil, etc. are mentioned, Among these, a dimethyl silicone oil is preferable. The silicone resin fine particles are silicone resin fine particles having a three-dimensional crosslinked structure, and methyl silicone resin is preferable as such a silicone resin. The particle size of the silicone resin fine particles is preferably 0.5 to 12 μm. Such silicone resin fine particles are available as “Tospearl” from GE Toshiba Silicone Co., Ltd.
By including these slidability improvers, the surface slidability can be improved.
In addition to the above components, as long as the physical properties of the components are not impaired, other additives commonly used during resin mixing and molding depending on the purpose, such as pigments, dyes, heat-resistant agents, stabilizers (antioxidants) Agents), weathering agents (ultraviolet absorbers), lubricants, mold release agents, crystal nucleating agents, plasticizers, fluidity improvers, impact modifiers, inorganic and organic antibacterial agents, etc. it can.

As a stabilizer, the phosphorus stabilizer marketed from each stabilizer maker as an antioxidant can be mentioned, for example. As commercial products, ADK STAB PEP-36, PEP-2
4, PEP-4C, PEP-8 (all are trademarks, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgafos 168 (trademark, manufactured by Ciba-Geigy), Sandstab P-EPQ (trademark, manufactured by Sandoz), Chelex L (Trademark, Sakai Chemical Industry Co., Ltd.) 3P2
S (trademark, manufactured by Ihara Chemical Industry Co., Ltd.), Mark 329K, Mark P (all are trademarks, manufactured by Asahi Denka Kogyo Co., Ltd.) and Weston 618 (trademark, manufactured by Sanko Chemical Co., Ltd.).

Other stabilizers include hindered phenol antioxidants, epoxy stabilizers, sulfur stabilizers and the like. Examples of the hindered phenol antioxidant include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate and 2,6-di-t-butyl-4-hydroxy. And methylphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like. . Examples of the epoxy stabilizer include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, and the like.

  The addition amount of these stabilizers is not particularly limited, but is preferably 0.0001 to 5 parts by weight with respect to 100 parts by weight as a total of components (A) to (D).

  Preferably, the release agent is a silicone release agent such as methylphenyl silicone oil, an ester release agent such as pentaerythritol tetrastearate, glycerol monostearate, montanic acid wax, poly α-olefin, or an olefin release. Agents and the like. The addition amount of these release agents is not particularly limited, but is preferably 0.0001 to 5 parts by weight with respect to 100 parts by weight as a total of components (A) to (D).

As the UV absorber, a UV absorber commonly used in polycarbonate resin compositions can be used. For example, a benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, a salicylate type ultraviolet absorber and the like can be mentioned. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3' , 5'-Gee
Amylphenyl) benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-)
Methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl)- 6- (2H-benzotriazol-2-yl) phenol] and the like. A benzotriazole-based ultraviolet absorber is commercially available, for example, as UV5411 from American Cyanamid. A benzophenone ultraviolet absorber is commercially available as UV531 from Sinamid. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

  The addition amount of these ultraviolet absorbers is not particularly limited, but is preferably 0.0001 to 5 parts by weight with respect to 100 parts by weight of the total of components (A) to (D). Moreover, a compatibilizing agent can be added to the thermoplastic resin composition according to the present invention.

Examples of the compatibilizer include a copolymer obtained by grafting an acrylonitrile-styrene copolymer onto a polycarbonate, or a copolymer obtained by grafting a polystyrene resin onto a polycarbonate. For example, Modeler C H430, L430D, and L150D manufactured by NOF Corporation. It is commercially available. Polymethyl methacrylate (PMMA) can also be used as a compatibilizing agent. The amount of these compatibilizers to be added is not particularly limited, but is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight as a total of components (A) to (D).

As the impact modifier, in the presence of rubber containing a repeating unit derived from butadiene, two or more monomers selected from the group consisting of methacrylic acid esters, acrylic acid esters and aromatic vinyl compounds are copolymerized. What is obtained is mentioned. Examples of the rubber containing a repeating unit derived from butadiene include polybutadiene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, and a butadiene-acrylic acid ester copolymer. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and octyl methacrylate. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, and the like. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Such elastic copolymers are commercially available and can be easily obtained. Examples include Kane Ace B series of Kaneka Chemical Co., Ltd., Metabrene C series of Mitsubishi Rayon Co., Ltd., EXL series, HIA series, BTA series, KCA series of Kureha Chemical Industry Co., Ltd., and the like.
In addition, one or two or more vinyl monomers are graft-polymerized to a composite rubber having a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component cannot be separated from each other. In addition, composite rubber-based graft polymers are also included, and when such graft polymers are used, better flame retardancy and impact resistance can be obtained and preferably used. Among such composite rubber-based graft copolymers, as a particularly preferable one, Methbrene S-2001 is preferably used from Mitsubishi Rayon Co., Ltd.
In addition, it is desirable that the composition according to the present invention does not substantially contain a styrene butadiene acrylonitrile (ABS) resin component.

  When the ABS resin component is contained, the formed product may be easily scraped or the flame retardancy may be reduced.

  Conventionally, an antistatic material has been added to an alloy of a polycarbonate and an ABS resin component. However, such a composition has limitations in terms of sliding characteristics and the like, and is a media-based housing as in the present invention. In some cases, it is difficult to use for molded articles such as cases.

  There is no restriction | limiting in particular in the method for manufacturing the resin composition of this invention, A normal method can be used satisfactorily. In general, the melt mixing method is desirable. Although a small amount of solvent can be used, it is generally not necessary.

  As an apparatus, an extruder, a Banbury mixer, a roller, a kneader, etc. can be mentioned as an example. These devices can be operated batchwise or continuously. Moreover, the mixing order of components is not particularly limited.

For example, when melt-kneading with an extruder or the like, all the components may be blended and kneaded, or a plurality of feed ports may be provided in one extruder and one or more types of each component may be fed sequentially along the cylinder. May be. The resin composition obtained by melt-kneading may be used immediately for production of the molded product according to the present invention, or after cooling and solidification to form pellets, powders, etc., and adding additives as necessary And may be melted again.
[Molded body]
The molding method that has been applied to conventional polycarbonate resin compositions can be applied to the polycarbonate resin composition of the present invention without any particular limitation. As the molding method, a known molding method such as injection molding, extrusion molding, vacuum / pressure molding or the like can be employed.

  The molded body made of such a polycarbonate resin composition according to the present invention uses optical disks for recording data, information, music, video, etc., that is, tape type data cartridges, optical disks, magnetic disks, blue lasers. It is particularly suitable as an external or internal mechanism plastics part, that is, a casing or a housing of a magnetic disk, a device using a current DVD reading mechanism, a magnetic disk, an electronic / electrical device, a household device, or an OA device. Home appliances, OA equipment, electrical and electronic parts include TV housing, TV chassis, deflection yoke, other TV parts, AC adapter, power box, air conditioner parts, audio parts, lighting cover, monitor housing, monitor chassis, notebook PC housing, notebook PC battery case, LCD projector housing, PDA housing, antenna cover, printer housing, printer chassis, toner cartridge, ink tank, paper feed tray, scanner housing, scanner frame, mobile phone housing, mobile phone Examples include battery cases.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(A) Polycarbonate resin (PC):
As the polycarbonate, Lexan 101 (trade name) manufactured by GE Plastics was used.
(B) Antistatic material:
The antistatic material used was Pelestat NC6321 (trade name) manufactured by Sanyo Chemical Industries.
(C) Phosphorus flame retardant:
As the phosphorus flame retardant, CR741-S (trade name) manufactured by Daihachi Chemical Industry Co., Ltd. was used.
(D) Polytetrafluoroethylene (PTFE):
PTFE used was Lebron L-5 (trade name) manufactured by Daikin Industries.
(E) Inorganic filler:
As the inorganic filler, talc LMS200 (trade name) manufactured by Tsuchiya Kaolin Co., Ltd. was used.
(F) ABS resin:
As the ABS resin, SANTAC AT07 manufactured by Mitsui Chemicals was used.
(G) Stabilizer:
As a stabilizer, ADK STAB AO-50 manufactured by Asahi Denka Co., Ltd. was used.

  In Examples and Comparative Examples, evaluation was performed as follows.

[Examples 1 to 3, Comparative Examples 1 to 5]
Each component was melt kneaded at a ratio (weight ratio) shown in Table 1 using a 40 mm twin screw extruder at a kneading preset temperature of 250 ° C., a screw rotation speed of 300 rpm, and an output amount of 150 kg / h.
Pellet was made. Using this pellet, a test piece was molded under the conditions of a set temperature of 250 ° C. and a mold temperature of 50 ° C. by an injection molding machine manufactured by Toyo Kikai Kogyo. The following characteristics evaluation was performed about the obtained test piece. The results are shown in Table 1.
Physical property test (1) Surface resistance value: According to ASTM D257, a test piece of 50 mm × 50 mm × 3.2 mm was measured at a charge of 100V.
(2) Half-life: measured at an applied voltage of 9.0 KV according to JIS L 1094.
(3) IZOD impact test with notch: according to ASTM D256, room temperature 23 ° C., humidity 50%
Measured in a controlled room.
(4) Flexural modulus test: measured in accordance with ASTM D790.
(5) Sliding wear test: Using a thrust type wear tester, the weight loss% was measured using a counterpart member stainless steel S45C with a load of 2.5 kg / cm ² , a rotation speed of 300 mm / second, and 6 hours.
(6) Melt flow index (MFI): Measured at 260 ° C. and 2.16 kg load according to ASTM D1238.
(7) Flame retardancy test: According to the test method of UL94V, a combustion test was performed with a test piece thickness of 1.0 mm, and the ability of UL94V was confirmed.

  The results are shown in Table 1.

  From Table 1, the molded product formed from the composition obtained in the example has a low surface resistance and a short half-life. For this reason, it turns out that it is excellent in lasting antistatic performance.

Moreover, since the weight loss of the sliding wear test is small, the molded product of the example is excellent in sliding property and wear resistance. On the other hand, Comparative Example 3 having a different composition and Comparative Examples 4 and 5 containing ABS resin are very easy to scrape and have poor wear resistance and slidability.

  Furthermore, the molded articles of the examples have high flame retardancy and have flame retardancy satisfying UL94V2.

  Moreover, since the molded article of an Example has the impact strength and bending elastic modulus comparable as the molded article of a comparative example, it turns out that it has the same mechanical strength.

As described above, according to the present invention, since it has a specific composition, it has high mechanical strength, high flame retardancy, excellent persistent antistatic properties, and excellent sliding properties and wear resistance. Can be obtained.

Claims (10)

(A) aromatic polycarbonate resin, (B) persistent antistatic material, (C) phosphorus flame retardant, (D) fluorine compound, and the total of (A) to (D) is 100% by weight When
(A) Aromatic polycarbonate resin: 10 to 98% by weight,
(B) Persistent antistatic material: 1 to 30% by weight,
(C) Phosphorus flame retardant: 1 to 30% by weight,
(D) Fluorine compound: 0 to 30% by weight,
A long-lasting antistatic polycarbonate-based resin composition satisfying V-2 in the UL standard 94V test, characterized in that (A) Aromatic polycarbonate resin, (B) persistent antistatic material, (C) phosphorus flame retardant, (D) fluorine compound, and the total of (A) to (D) is 100% by weight And when
(A) Aromatic polycarbonate resin: 10 to 98% by weight,
(B) Persistent antistatic material: 1 to 30% by weight,
(C) Phosphorus flame retardant: 1 to 30% by weight
(D) fluorinated compound: in the range of 0 to 30% by weight,
In addition, when the total of (A) to (D) is 100% by weight, (E) the inorganic filler is contained in an amount of more than 0 and not more than 40% by weight. 2, a long-lasting antistatic polycarbonate resin composition.   (B) Persistent antistatic materials include polyetheresters, polyethylene glycol polyamides or polyesteramides, polyethylene glycol methacrylate copolymers, poly (ethylene oxide / propylene oxide) copolymers, poly (epichlorohydrin) / Ethylene oxide) copolymers, quaternary ammonium base-containing methacrylate copolymers, and at least one selected from the group consisting of high molecular weight polyethylene glycols. The long-lasting antistatic polycarbonate resin composition described in 1. The long-lasting antistatic polycarbonate resin composition according to any one of claims 1 to 2, wherein (C) the phosphorus-based flame retardant is at least one selected from phosphate ester-based flame retardants. 3. The long-lasting antistatic polycarbonate resin according to claim 1, wherein the fluorine-based compound is a polytetrafluoroethylene resin having a sliding wear resistance and a molecular weight of 3 million to 10 million. Composition. (E) Inorganic filler is talc, mica, barium sulfate, glass fiber, hollow glass fiber,
3. The sustain according to claim 2, which is at least one selected from carbon fibers, hollow carbon fibers, titanium oxide whiskers, fibrous wollastonite, clay, silica, glass flakes, glass beads, and hollow fillers. Antistatic polycarbonate resin composition. The durable antistatic polycarbonate resin composition according to any one of claims 1 to 6, wherein the resin composition does not substantially contain a styrene butadiene acrylonitrile (ABS) resin component. The fluorine-based compound does not have fibril-forming ability.
7. The durable antistatic polycarbonate resin composition according to any one of 7 above.   A molded article comprising the resin composition according to claim 1. 10. The molded product is an optical mechanism for recording data, information, music, video, etc., a magnetic disk, an electronic device, a household device, or an external mechanism or an internal mechanism plastic part of an OA device. The molded product described.